JP2003098616A - Silver halide emulsion and silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide emulsion that causes neither lowering of sensitivity nor lowering of contrast even in digital exposure such as laser scanning exposure, has high sensitivity and gives high-contrast gradation and to provide a silver halide photographic sensitive material using the emulsion. SOLUTION: In the silver halide emulsion, the coefficient of variation in equivalent spherical diameter of all grains is <=20% and >=50% of the total projected area of all the grains is occupied by silver halide grains having <=0.4 μm equivalent spherical diameter and >=90 mol.% silver chloride content and having a silver bromide-containing phase and/or a silver iodide-containing phase in a layered state. The silver halide photographic sensitive material contains the silver halide emulsion.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide emulsion and a silver halide photographic light-sensitive material, and more particularly, it is suitable for rapid processing, and can obtain high sensitivity and high gradation even in digital exposure such as laser scanning exposure. And a silver halide photographic light-sensitive material using the silver halide emulsion.

[0002]

2. Description of the Related Art In recent years, digitalization has been remarkably permeated even in the field of color printing using color photographic paper. For example, the digital exposure method by laser scanning exposure can be applied to a color printer from a processed color negative film which has been conventionally used. Compared to the analog exposure method that directly prints, it shows a dramatic increase in the penetration rate. Such a digital exposure method is characterized in that a high image quality can be obtained by performing image processing, and plays an extremely important role in improving the quality of color prints using color printing paper. Further, with the rapid spread of digital cameras, it is also an important factor that color prints of high image quality can be easily obtained from these electronic recording media, and it is considered that these will lead to further dramatic spread.

On the other hand, as the color printing method, techniques such as an ink jet method, a sublimation method, and a color xerography have made progress, and the color printing method is being recognized as a color printing method. Among these, the characteristics of the digital exposure method using color photographic paper are high image quality, high productivity, and high image fastness, and by utilizing these characteristics, it is possible to produce higher quality photos more easily and more. It is desired to provide it at low cost.

As a silver halide emulsion used for color photographic paper, a silver halide emulsion having a high silver chloride content is used mainly because of the demand for rapid processability for enhancing productivity. In particular, when a silver halide emulsion having a small grain size and a high silver chloride content is used, rapid processability is further improved, and high color development efficiency makes it possible to provide a low-cost color photographic paper. .. From this,
Increasing the performance of small grain size, high silver chloride silver halide emulsions is important to enable high quality photographs to be provided more easily and at lower cost.
However, such a silver halide emulsion having a small grain size and a high content of silver chloride has a problem in that it has a low sensitivity and is likely to cause a low softness in a high illuminance exposure such as a laser scanning exposure. In addition, in order to quickly return the color print, it is important to develop the product in a short time after exposure in a minilab system. There is a problem that the latent image stability is poor from 10 to several tens of seconds.

It is known to dope iridium to improve the high intensity failure of silver chloride emulsions. However, iridium-doped silver chloride emulsions are known to cause latent image sensitization within a short period of time after exposure. For example, Japanese Patent Publication No. 34103/1995 discloses a high silver bromide content. It is disclosed that the problem of latent image sensitization is solved by providing a localized phase and doping it with iridium. The silver halide emulsion prepared by this method is 1/10
High sensitivity and high contrast even with relatively high illuminance of about 0 seconds, and there is no problem of latent image sensitization, but let's maintain high sensitivity up to the ultrahigh illuminance of 1 microsecond required by the digital exposure method by laser scanning exposure. Then, it became clear that it is difficult to obtain a hard gradation. Further, US Pat. No. 5,691,119 discloses a method for preparing an emulsion having a localized phase having a high silver bromide content, which hardens a high illuminance gradation. It has a drawback that the effect is not sufficient and the performance is not stable with repeated preparation.

At least 3, in US Pat. Nos. 5,783,373 and 5,783,378.
A method for reducing high light intensity failure and increasing contrast by using a dopant of a kind is disclosed. However, the reason that a hard gradation can be obtained is that a dopant having a desensitizing and hardening effect is used, which is in principle incompatible with the high sensitivity.

US Pat. Nos. 5,726,005 and 5,736,310 disclose high sensitivity by using an I-containing emulsion having a concentration maximum on the sub-surface of a high silver chloride emulsion. It is disclosed that an emulsion with high illumination intensity can be obtained. In the example of European Patent EP 0,928,988A, the side length of 0.218 μm in which the I band was formed at 93% of the particle formation, that is, the equivalent spherical diameter was about 0.
It is disclosed that an emulsion excellent in reciprocity law failure, temperature dependence during exposure and pressure characteristics can be obtained by incorporating a specific compound into 27 μm grains. However, silver halide emulsions with a small grain size and a high content of silver chloride as shown in these can certainly obtain higher sensitivity as high-intensity exposure, but ultra-high-intensity exposure such as laser scanning exposure It has been found that the gradation is very soft, it is not suitable for digital exposure with a limited dynamic range of light quantity, and the latent image stability is poor from several seconds to several tens of seconds after exposure.

JP-A-58-95736 and 58-
No. 108533, No. 60-222844, No. 60-222845, No. 62-253143, No. 62-253144, and No. 62-25316.
6 gazette, the same 62-254139 gazette, the same 63-46.
No. 440, No. 63-46441, No. 63-8.
9840, U.S. Pat. Nos. 4,820,624, 4,865,962, and 5,39.
No. 9,475, No. 5,284,743, etc., high sensitivity is obtained by locally containing a phase having a high silver bromide content in various forms in an emulsion having a high silver chloride content. Is disclosed. However, with a silver halide emulsion containing a silver bromide-containing phase and / or a silver iodide-containing phase and having a small grain size and a high silver chloride content, a specific contrast enhancement effect in ultra-high-intensity exposure such as laser scanning exposure is obtained. There is no disclosure.

US Pat. No. 5,049,485 discloses that high sensitivity can be obtained by chemically sensitizing an Au (I) compound coordinated with a mesoion.
US Pat. No. 5,945,270 discloses that high sensitivity can be obtained by chemically sensitizing with an Au (I) compound in which a mercapto having a water-soluble group is coordinated. . It is known that these are relatively stable Au (I) compounds, but they are emulsions containing a silver bromide-containing phase and / or a silver iodide-containing phase, and have a specific contrast-increasing effect in high-illuminance exposure. There is no disclosure.

[0010]

The first problem to be solved by the present invention is that even in digital exposure such as laser scanning exposure, high sensitivity and high gradation can be obtained without lowering sensitivity or softening. To provide a silver halide emulsion obtained and a silver halide photographic light-sensitive material using the same. Further, a second problem to be solved by the present invention is to provide a silver halide photographic light-sensitive material which is excellent in rapid processability and can be produced at a low cost due to high coloring efficiency.

[0011]

Means for solving the problems Means for solving the above problems are as follows. That is, <1> The variation coefficient of the sphere-equivalent diameter of all particles is 20% or less, the sphere-equivalent diameter is 0.4 μm or less, the silver bromide-containing phase is formed in a layered form, and the silver chloride-containing phase is contained. A silver halide emulsion characterized in that silver halide grains having a ratio of 90 mol% or more occupy 50% or more of the total projected area of all the grains. <2> The silver halide emulsion according to <1>, wherein the silver bromide-containing phase is a silver bromide-containing phase having a maximum silver bromide concentration inside a grain. <3> The variation coefficient of the sphere-equivalent diameter of all grains is 20% or less, the sphere-equivalent diameter is 0.4 μm or less, the silver iodide-containing phase is formed in layers, and the silver chloride content is A silver halide emulsion characterized in that silver halide grains of 90 mol% or more account for 50% or more of the total projected area of all the grains. <4> The silver halide emulsion according to <3>, wherein the silver iodide-containing phase is a silver iodide-containing phase having a maximum silver iodide concentration on the grain surface. <5> The variation coefficient of the equivalent sphere diameter of all grains is 20% or less, the equivalent sphere diameter is 0.4 μm or less, and the silver bromide-containing phase and the silver iodide-containing phase are formed in layers. A silver halide emulsion characterized in that silver halide grains having a silver chloride content of 90 mol% or more occupy 50% or more of the total projected area of the grains. <6> The silver halide emulsion according to <5>, wherein the silver bromide-containing phase is formed inside the grains more than the silver iodide-containing phase. <7> The silver halide emulsion according to any one of <1> to <6>, wherein the silver halide grains are cubic or tetradecahedral grains. <8> The electron slow-release time of the silver halide grains is 10 ^−5.
The silver halide emulsion according to any one of <1> to <7>, which is from 10 seconds to 10 seconds. <9> The silver halide emulsion according to any one of <1> to <8>, wherein the silver halide grains include a hexacoordination complex having Ir as a central metal and having Cl, Br, or I as a ligand. is there. <10> The silver halide emulsion according to <9>, wherein the hexacoordinated complex is contained in the silver bromide-containing phase. <11> The silver halide according to any one of <1> to <10>, wherein the silver halide grain contains a hexacoordination complex having Ir as a central metal and having at least one ligand other than halogen and cyan. It is an emulsion. <12> The oxidation potential of the latent image of the silver halide emulsion is
The silver halide emulsion according to any one of <1> to <11>, which is nobler than 70 mV. <13> The silver halide emulsion according to any one of <1> to <12>, which is gold-sensitized. <14> The silver halide emulsion has a colloidal gold sulfide or gold complex stability constant log β ₂ of 21 or more and 3 or more.
The silver halide emulsion according to <13>, which is gold sensitized with a gold sensitizer of 5 or less. <15> A silver halide photographic light-sensitive material containing the silver halide emulsion according to any one of <1> to <14>.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.

[Silver Halide Emulsion] The silver halide emulsion of the present invention has a variation coefficient of equivalent sphere diameter of all grains of 20% or less and an equivalent sphere diameter of 0.4 μm or less, and silver bromide. A silver halide grain having a silver-iodide-containing phase and / or a silver iodide-containing phase formed in a layered form and having a silver chloride content of 90 mol% or more (hereinafter sometimes referred to as "specific silver halide grain") It occupies 50% or more of the total projected area of all the grains. Here, "all grains" means "all silver halide grains" contained in the silver halide emulsion of the present invention.
Means

The grain shape of the specific silver halide grains in the silver halide emulsion of the present invention is not particularly limited, but it is substantially cubic or tetradecahedral crystal grains having {100} faces (these grains have apex vertices). It may be rounded and may have a higher surface), octahedral crystal grains, the main surface of which is {10
It is preferably composed of tabular grains having an aspect ratio of 2 or more, which are composed of 0} planes or {111} planes. The aspect ratio is a value obtained by dividing the diameter of a circle corresponding to the projected area by the thickness of particles. In the present invention, cubic or tetradecahedral grains are more preferred.

The specific silver halide grains in the present invention contain silver chloride, and the content of the silver chloride must be 90 mol% or more. From the viewpoint of rapid processability,
The silver chloride content is preferably 93 mol% or more, and 95 mol%
The above is more preferable. Further, the specific silver halide grains need to contain silver bromide and / or silver iodide. The silver bromide content is preferably 0.1 to 7 mol% because it has high contrast and excellent latent image stability.
It is more preferably 0.5 to 5 mol%. The silver iodide content is preferably 0.02 to 1 mol% because it has high sensitivity and high contrast under exposure to high illuminance, and is 0.0
5 to 0.50 mol% is more preferable, and 0.07 to 0.4
0 mol% is most preferred. The specific silver halide grains of the present invention are preferably silver iodobromochloride grains,
Silver iodobromochloride grains having the above halogen composition are more preferred.

The specific silver halide grains in the silver halide emulsion of the present invention have a silver bromide-containing phase and / or a silver iodide-containing phase. Here, the silver bromide- or silver iodide-containing phase means a portion where the concentration of silver bromide or silver iodide is higher than that of the surrounding area. The halogen composition of the silver bromide-containing phase or silver iodide-containing phase and its surroundings may change continuously or may change sharply. Such a silver bromide- or silver iodide-containing phase may form a layer having a substantially constant width in a certain portion within the grain, or may be a maximum point having no spread. The local silver bromide content of the silver bromide-containing phase is 5
It is preferably at least mol%, more preferably from 10 to 80 mol%, and most preferably from 15 to 50 mol%. The local silver iodide content of the silver iodide-containing phase is preferably 0.3 mol% or more,
It is more preferably 8 mol% and most preferably 1 to 5 mol%. A plurality of such silver bromide- or silver iodide-containing phases may be layered in each grain, and the respective silver bromide or silver iodide content may differ, but at least one of One contained phase,
It should preferably have at least one containing phase each.

It is important that the silver bromide-containing phase or silver iodide-containing phase of the silver halide emulsion of the present invention is in a layered form so as to surround the grains. One of the preferred embodiments is that the silver bromide-containing phase or the silver iodide-containing phase formed in a layer surrounding the grains has a uniform concentration distribution in the orbiting direction of the grains in each phase. However, in the silver bromide-containing phase or the silver iodide-containing phase that is layered so as to surround the grain, the maximum or minimum point of the silver bromide or silver iodide concentration exists in the orbiting direction of the grain, and the concentration distribution May have. For example, when the layer has a silver bromide-containing phase or a silver iodide-containing phase in the vicinity of the grain surface so as to surround the grain, the concentration of silver bromide or silver iodide at the corner or edge of the grain is different from that on the main surface. There are cases. Further, apart from the silver bromide-containing phase and the silver iodide-containing phase which are layered so as to surround the grain, the silver bromide-containing phase which is completely isolated and exists in a specific part of the surface of the grain and does not surround the grain. Alternatively, there may be a silver iodide-containing phase.

When the silver halide emulsion of the present invention contains a silver bromide-containing phase, the silver bromide-containing phase is preferably formed in layers so that the silver bromide-containing phase has a maximum silver bromide concentration inside the grain. . When the silver halide emulsion of the present invention contains a silver iodide-containing phase, the silver iodide-containing phase is preferably formed in layers so that the grain surface has a maximum silver iodide concentration. Such a silver bromide-containing phase or a silver iodide-containing phase is composed of 3% or more and 30% or less of the grain volume in terms of increasing the local concentration with a smaller silver bromide or silver iodide content. Preferably 3% or more 1
It is more preferable that the amount of silver is 5% or less.

The silver halide emulsion of the present invention preferably contains both a silver bromide-containing phase and a silver iodide-containing phase. In that case, the silver bromide-containing phase and the silver iodide-containing phase may be at the same place or different places in the grain, but if they are at different places, it is easier to control grain formation. preferable. Further, the silver bromide-containing phase may contain silver iodide, and conversely, the silver iodide-containing phase may contain silver bromide. In general,
The iodide added during the formation of high silver chloride grains is more likely to exude to the grain surface than bromide, so that the silver iodide-containing phase is likely to form near the grain surface. Therefore, when the silver bromide-containing phase and the silver iodide-containing phase are at different positions in the grain, it is preferable that the silver bromide-containing phase is formed inside the silver iodide-containing phase.
In such a case, another silver bromide-containing phase may be provided further outside the silver iodide-containing phase near the grain surface.

The silver bromide content or silver iodide content necessary for exhibiting the effects of the present invention, such as high sensitivity and high contrast, is the silver bromide-containing phase or silver iodide-containing phase inside the grain. The more it is formed, the more it increases, and the silver chloride content may be unnecessarily reduced to impair the rapid processability. Therefore, it is preferable that the silver bromide-containing phase and the silver iodide-containing phase are adjacent to each other in order to concentrate these functions for controlling the photographic effect near the surface in the grain. From these points, the silver bromide-containing phase is 50% to 100% of the grain volume measured from the inside.
It is preferable that the silver iodide-containing phase is formed at any of positions from 85% to 100% of the grain volume. Further, it is preferable that the silver bromide-containing phase is formed anywhere from 70% to 95% of the grain volume, and the silver iodide-containing phase is formed anywhere from 90% to 100% of the grain volume. preferable.

The introduction of the bromide or iodide ion for containing silver bromide or silver iodide in the silver halide emulsion of the present invention can be carried out by adding a solution of bromide salt or iodide salt alone, or by adding silver salt. A bromide salt or iodide salt solution may be added together with the addition of the solution and the high chloride salt solution. In the latter case, the bromide salt or iodide salt solution and the high chloride salt solution may be added separately or as a mixed solution of the bromide salt or iodide salt and the high chloride salt. The bromide salt or iodide salt is added in the form of a soluble salt such as an alkali or alkaline earth bromide salt or iodide salt. Alternatively, it can be introduced by cleaving bromide ion or iodide ion from the organic molecule described in US Pat. No. 5,389,508. Fine silver bromide grains or fine silver iodide grains can also be used as another bromide or iodide ion source.

The addition of the bromide salt or iodide salt solution is
The particle formation may be concentrated in one period, or may be performed over a certain period. The position of introduction of iodide ions into the high chloride emulsion is limited in order to obtain an emulsion having high sensitivity and low fog. When the iodide ion is introduced inside the emulsion grains, the increase in sensitivity is small. Therefore, the addition of the iodide salt solution is preferably performed outside 50% of the grain volume, more preferably outside 70%, and most preferably outside 85%. The addition of the iodide salt solution is preferably completed within 98% of the grain volume, and most preferably within 96%. When the addition of the iodide salt solution is completed slightly inside the grain surface, an emulsion having higher sensitivity and lower fog can be obtained. On the other hand, the bromide salt solution is preferably added to the outside of 50% of the grain volume, more preferably outside of 70%.

The distribution of the bromide or iodide ion concentration in the grain in the depth direction is determined by etching / TOF-SIMS.
(Time of Flight-Secondary
Ion Mass Spectrometry) method, for example, using TRIFTII type TOF-SIMS manufactured by Phi Evans. TOF-SIM
Regarding the S method, specifically, “Surface Analysis Technology Selection Manual, Secondary Ion Mass Spectrometry” edited by The Surface Science Society of Japan, Maruzen Co., Ltd. (1
999). Etching / TOF
When the emulsion grains are analyzed by the SIMS method, it can be analyzed that the iodide ions are exuded toward the grain surface even after the addition of the iodide salt solution is completed inside the grains. In the emulsion of the present invention, it is preferable that the iodide ion has a maximum concentration on the surface of the grain and the iodide ion concentration is attenuated toward the inner side in the analysis by the etching / TOF-SIMS method. It is preferable to have a maximum concentration inside. The local concentration of silver bromide can also be measured by an X-ray diffraction method if the silver bromide content is high to some extent.

In the present specification, the equivalent sphere diameter of a particle is represented by the diameter of a sphere having a volume equal to that of each particle. The silver halide emulsion of the present invention preferably comprises grains having a monodisperse grain size distribution. The variation coefficient of the spherical equivalent diameter of all grains contained in the silver halide emulsion of the present invention is 2
It is necessary to be 0% or less, more preferably 15% or less, and further preferably 10% or less. The coefficient of variation of the sphere-equivalent diameter is expressed as a percentage of the standard deviation of the sphere-equivalent diameter of each particle with respect to the average of the sphere-equivalent diameters.
At this time, it is also preferable to use the above monodisperse emulsion by blending it in the same layer for the purpose of obtaining a wide latitude, or to perform multi-layer coating.

The spherical equivalent diameter of the specific silver halide grains contained in the silver halide emulsion of the present invention is required to be 0.4 μm or less, preferably 0.35 μm or less, and 0.3 μm. The following is more preferable. The lower limit of the equivalent spherical diameter of silver halide grains is 0.05 μm.
m is preferable, and 0.1 μm is more preferable. A particle having a spherical equivalent diameter of 0.4 μm corresponds to a cubic particle having a side length of about 0.32 μm, and a particle having a spherical equivalent diameter of 0.35 μm has a side length of about 0.2.
Corresponding to cubic particles having a diameter of 8 μm, particles having an equivalent spherical diameter of 0.3 μm correspond to cubic particles having a side length of about 0.24 μm. The silver halide emulsion of the present invention may contain silver halide grains other than the specific silver halide grains. However, in the silver halide emulsion of the present invention, it is necessary that 50% or more of the total projected area of all silver halide grains is specific silver halide grains, and preferably 80% or more, It is more preferably 90% or more.

The sustained electron release time of the silver halide emulsion of the present invention is preferably between 10 ^-5 seconds and 10 seconds. Here, the term "electron sustained release time" refers to the time until a photoelectron generated in a silver halide crystal is trapped in an electron trap in the crystal and exposed again when the silver halide emulsion is exposed to light. . If the electronic controlled release time is shorter than 10 ^-5 seconds, it is difficult to obtain a high-sensitivity and high-contrast gradation in high-illuminance exposure. Cause The electron sustained release time is more preferably 10 ⁻⁴ to 10 seconds, most preferably 10 ⁻³ to 1 second.

The sustained electron release time can be measured by the double pulse photoconductivity method. A microwave photoconductivity method or a radio wave photoconductivity method is used to perform a first short-time exposure and then a second fixed short-time exposure. Electrons are trapped in the electron trap in the silver halide crystal by the first exposure, and when the second exposure is given immediately after that, the electron trap is clogged and the second photoconduction signal becomes large. If the two exposure intervals are set sufficiently and the electrons trapped in the electron trap have already been emitted in the first exposure, the photoconduction signal of the second emission returns to the original magnitude. If the exposure interval dependency of the second photoconductive signal intensity is taken by changing the exposure interval of two times, it becomes 2
It is possible to measure how the intensity of the photoconductive signal of the eye is decreasing. This represents the sustained release time of photoelectrons from the electron trap. The sustained release of electrons may continue to occur for a certain period of time after the exposure, but it is preferable that the sustained release is observed within 10 ⁻⁵ seconds to 10 seconds. 10 ^-4 seconds to 10
More preferably, sustained release is observed during 10 seconds, 10 ⁻³
More preferably, sustained release is observed between seconds and 1 second.

The specific silver halide grains in the silver halide emulsion of the present invention preferably contain iridium. The iridium preferably forms an iridium complex, and a 6-coordination complex having 6 ligands and iridium as a central metal is preferable because it can be uniformly incorporated into a silver halide crystal. One preferable embodiment of iridium used in the present invention is Cl, Br.
Alternatively, Ir having I as a ligand has Ir as a central metal 6
Coordination complexes are preferred, with all 6 ligands being Cl, Br
Alternatively, a hexacoordinated complex of Ir having Ir as a central metal is more preferable. In this case, Cl, Br or I in the hexacoordination complex
May be mixed. It is particularly preferable that the hexacoordinated complex having Cl, Br or I as a ligand and having Ir as the central metal is contained in the silver bromide-containing phase in order to obtain a hard gradation by exposure to high illuminance.

In the following, all six ligands are Cl, Br
Specific examples of the hexacoordinated complex of I or Ir having Ir as a central metal are shown below, but the iridium in the present invention is not limited thereto. [IrCl ₆ ] ^2- [IrCl ₆ ] ^3- [IrBr ₆ ] ^2- [IrBr ₆ ] ^3- [IrI ₆ ] ^3-

As another preferred embodiment of iridium used in the present invention, a hexacoordinated complex having Ir as a central metal and having at least one ligand other than halogen and cyan is preferred, and H ₂ O, OH, O and OCN are preferred. , A tricoordinated complex having Ir as a central metal and having a thiazole or a substituted thiazole as a ligand, and at least one H
_A hexacoordinated complex in which ₂ O, OH, O, OCN, thiazole or substituted thiazole is used as a ligand and the remaining ligand is Cl, Br or I and Ir is a central metal is more preferable. Further, a hexacoordinated complex in which one or two 5-methylthiazoles are used as ligands and the remaining ligands are Cl, Br, or I and Ir is a central metal is most preferable.

In the following, at least one H ₂ O, OH,
Specific examples of the hexacoordinated complex having O, OCN, thiazole or substituted thiazole as a ligand and the remaining ligands consisting of Cl, Br or I and Ir as a central metal are given below.
Iridium in the present invention is not limited to these.

[Ir (H ₂ O) Cl ₅ ] ^2- [Ir (H ₂ O) ₂ Cl ₄ ] ^- [Ir (H ₂ O) Br ₅ ] ^2- [Ir (H ₂ O) ₂ Br ₄ ] _{^{- [Ir (OH) Cl 5}} ] 3- [Ir (OH) 2 Cl 4] 3- [Ir (OH) Br 5] 3- [Ir (OH) 2 Br 4] 3- [Ir (O) Cl 5 ] ^4- [Ir (O) ₂ Cl ₄ ] ^5- [Ir (O) Br ₅ ] ^4- [Ir (O) ₂ Br ₄ ] ^5- [Ir (OCN) Cl ₅ ] ^3- [Ir (OCN) ^{_{Br 5] 3- [Ir (thiazole}} ) Cl 5] 2- [Ir (thiazole) 2 Cl 4] - [Ir (thiazole) Br 5] 2- [Ir (thiazole) 2 Br 4] - [Ir (5- Methylthiazole) Cl ₅ ]
^2- [Ir (5-methylthiazole) ₂ Cl ₄ ]
^- [Ir (5-methylthiazole) Br ₅ ]
^2- [Ir (5-methylthiazole) ₂ Br ₄ ]
^-

The object of the present invention is that all 6 ligands are C
a hexacoordinated complex of 1, 1, Br or I having Ir as the central metal, or a hexacoordinated complex of Ir having at least one ligand other than halogen and cyan as the central metal,
It is preferably achieved by using either one alone. However, in order to further enhance the effect of the present invention, all 6 ligands are I, which consist of Cl, Br or I.
It is preferable to use a 6-coordination complex having r as a central metal and a 6-coordination complex having Ir as a central metal having at least one ligand other than halogen and cyan. Furthermore,
A hexacoordinated complex having at least one H ₂ O, OH, O, OCN, thiazole or substituted thiazole as a ligand and the rest of the ligands consisting of Cl, Br or I and having Ir as the central metal is 2 Kinds of ligands (H ₂ O,
It is preferable to use a complex composed of one of OH, O, OCN, thiazole or substituted thiazole and one of Cl, Br or I).

The metal complexes listed above are anions,
When a salt is formed with a cation, a counter cation which is easily dissolved in water is preferable. Specifically, alkali metal ions such as sodium ion, potassium ion, rubidium ion, cesium ion and lithium ion,
Ammonium ion and alkylammonium ion are preferred. In addition to water, these metal complexes should be dissolved in a suitable organic solvent that can be mixed with water (eg, alcohols, ethers, glycols, ketones, esters, amides, etc.) before use. You can These iridium complexes give 1 × per mole of silver during grain formation.
It is preferable to add 10 ^-10 mol to 1 × 10 ^-3 mol, and most preferably 1 × 10 ^-8 mol to 1 × 10 ^-5 mol.

In the present invention, the above iridium complex is
By adding directly to the reaction solution at the time of silver halide grain formation, or in an aqueous solution of a halide for forming silver halide grains, or in a solution other than that, and then adding to the grain formation reaction solution, the halogen It is preferably incorporated into silver halide grains. Further, it is also preferable to physically ripen fine particles in which an iridium complex has been incorporated into the grains and incorporate them into the silver halide grains. Further, these methods may be combined and contained in the silver halide grains.

When these complexes are incorporated into silver halide grains, they may be made to exist uniformly inside the grains. JP-A-4-208936 and JP-A-2-125
As disclosed in JP-A No. 245 and JP-A-3-188437, it is also preferable that the layer is present only in the particle surface layer, and the complex is present only inside the particle and a layer not containing the complex is added to the particle surface. Is also preferable. Moreover, US Pat. No. 5,252,451 and US Pat.
As disclosed in 6,530, it is also preferable to physically ripen the fine particles having the complex incorporated in the particles to modify the surface phase of the particles. Further, these methods may be used in combination, and plural kinds of complexes may be incorporated in one silver halide grain. There is no particular limitation on the halogen composition at the position where the above complex is contained, but a hexacoordinated complex in which all six ligands are Cl, Br or I and whose central metal is Ir has a silver bromide concentration maximum part. It is preferable to contain it.

In the present invention, in addition to iridium, other metal ions can be doped inside and / or on the surface of the silver halide grain. The metal ion used is preferably a transition metal ion, of which iron, ruthenium, osmium, lead, cadmium, or zinc is preferable. Further, these metal ions are more preferably used as a hexacoordinate octahedral complex with a ligand. When an inorganic compound is used as a ligand, cyanide ion, halide ion, thiocyanate, hydroxide ion, peroxide ion, azide ion, nitrite ion, water, ammonia, nitrosyl ion, or thiol ion. It is preferable to use a nitrosyl ion, and the above iron,
It is also preferable to use it by coordinating with any metal ion of ruthenium, osmium, lead, cadmium, or zinc, and it is also preferable to use plural kinds of ligands in one complex molecule. Further, an organic compound can be used as the ligand, and a preferable organic compound has a main chain having 5 carbon atoms.
The following chain compounds and / or 5-membered or 6-membered heterocyclic compounds can be mentioned. More preferable organic compound is a compound having a nitrogen atom, a phosphorus atom, an oxygen atom, or a sulfur atom in the molecule as a coordination atom for a metal, and particularly preferably furan, thiophene, oxazole, isoxazole, thiazole, isothiazole. ,
Imidazole, pyrazole, triazole, furazan,
Pyran, pyridine, pyridazine, pyrimidine, and pyrazine, and compounds in which a substituent is introduced into these compounds as a basic skeleton are also preferable.

The combination of a metal ion and a ligand is preferably an iron ion or a ruthenium ion and a cyanide ion. In the present invention, it is preferable to use iridium and these compounds in combination. In these compounds, the cyanide ion preferably occupies the majority of the coordination numbers with respect to the central metal iron or ruthenium, and the remaining coordination sites are thiocyan, ammonia, water, nitrosyl ion, dimethyl sulfoxide, pyridine, It is preferably occupied by pyrazine or 4,4′-bipyridine. Most preferably, all six coordination sites of the central metal are occupied by cyanide ions to form a hexacyanoiron complex or hexacyanoruthenium complex. It is preferable to add 1 × 10 ⁻⁸ to 1 × 10 ⁻² mol of each complex containing cyanide ion as a ligand per 1 mol of silver during grain formation, preferably 1 × 10 ^−6.
It is most preferable to add from 5 to 10 ^-4 mol.
When ruthenium and osmium are the central metals, it is also preferable to use nitrosyl ion, thionitrosyl ion, or water molecule and chloride ion together as ligands. It is more preferable to form a pentachloronitrosyl complex, a pentachlorothionitrosyl complex, or a pentachloroaqua complex, and it is also preferable to form a hexachloro complex. These complexes are preferably added in an amount of 1 × 10 ⁻¹⁰ to 1 × 10 ⁻⁶ mol, and more preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻⁶ mol per mol of silver during grain formation. That is.

The oxidation potential of the latent image of the silver halide emulsion of the present invention is preferably nobler than 70 mV and 100 m.
More preferably, it is noble than V. The oxidation potential of the latent image being nobler than 70 mV means that the latent image has relatively strong oxidation resistance. Oxidation potential of latent image is based on Photographic Sensitivity- (Photo
graphic Sensitivity, Oxford
d University Press, Tadaak
i Tani 1995) 103, page 103 and the like. Specifically, the silver halide emulsion coating is subjected to gradation exposure for 0.1 seconds,
Before development, the latent image is bleached by immersing it in a redox bath of various potentials.

The silver halide emulsion of the present invention is usually chemically sensitized. In the chemical sensitization method, sulfur sensitization typified by the addition of an unstable sulfur compound, noble metal sensitization typified by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As the compound used for the chemical sensitization, those described in JP-A-62-215272, from page 18, lower right column to page 22, upper right column are preferably used. Of these, gold-sensitized ones are particularly preferable. By performing gold sensitization, it is possible to further reduce fluctuations in photographic performance when scanning and exposing with laser light or the like.

In order to perform gold sensitization on the silver halide emulsion of the present invention, various inorganic gold compounds, gold (I) complexes having inorganic ligands and gold (I) compounds having organic ligands are used. can do. Examples of the inorganic gold compound include chloroauric acid or a salt thereof, and examples of the gold (I) complex having an inorganic ligand include a gold dithiocyanate compound such as potassium gold (I) dithiocyanate and gold (I) 3 dithiosulfate. Compounds such as sodium dithiosulfate compounds such as sodium can be used.

The silver halide emulsion of the present invention is colloidal.
Gold sulfide or gold complex stability constant log β₂Is 21 or more
And it is preferable that it is gold sensitized with a gold sensitizer of 35 or less.
Good The research method for producing colloidal gold sulfide is
Closure (Research Disclosur)
e, 37154), Solid State Ionics
(Solid State Ionics) No. 79
Vol. 60-66, 1995, Compt. Ren
d. Hebt. Seans Acad. Sci. S
ect. B Vol. 263, p. 1328, published in 1966
Have been described. Various sizes as colloidal gold sulfide
It is possible to use those with a particle size of 50 nm or less.
You can The amount added can vary widely depending on the case
Is 5 × 10 5 as gold atom per mol of silver halide.^-7
~ 5 x 10^-3Mol, preferably 5 × 10 ^-6~ 5 x 10^-Four
It is a mole. In the present invention, gold sensitization is further sensitized.
Methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization
Sensitivity or combination with precious metal sensitization using other than gold compounds
You may let me.

Below, the gold complex stability constant log β ₂ is 2
The gold sensitizer of 1 or more and 35 or less will be described. The complex stability constant log β ₂ of gold is measured by a comprehensive
Coordination Chemistry (Compreh
intensive Coordination Chemis
try, Chapter 55, p.864, 1987), Encyclopedia of Electrochemistry of.
The Elements (Encyclopedia of E
electrochemistry of the El
elements, Chapter IV-3, 1975), Journal of the Royal Chemical Society (Journal of the Roy).
al Netherlands Chemical S
(Vol. 101, 164, 1982), and the measurement methods described in the references thereof, and the measurement temperature is 25 ° C. and pH is potassium dihydrogen phosphate / disodium hydrogen phosphate buffer. The ionic strength was adjusted to 6.0 from the value of the gold potential under the condition of 0.1 M (KBr).
The value of gβ ₂ can be calculated. In this measurement method, the value of log β ₂ of thiocyanate ion is 20.5.
And the literature (Comprehensive Coordination Chemistry (Comprehensive Co
coordination Chemistry, 1987
Year, Chapter 55, page 864, Table 2)) described values, values close to 20 are obtained.

Gold complex stability constant log β in the present invention
The gold sensitizer in which ₂ is 21 or more and 35 or less is preferably represented by the following general formula (I). General formula (I)
{(L ¹ ) _x (Au) _y (L ² ) _z · Q _q } _p

In the general formula (I), L ¹ and L ² each independently represent a compound having a logβ ₂ value of 21 to 35. The compound contained in 22 to 31 is preferable, and the compound contained in 24 to 28 is more preferable.

L ¹ and L ² are, for example, compounds containing at least one unstable sulfur group capable of reacting with silver halide to form silver sulfide, hydantoin compounds, thioether compounds, mesoionic compounds, —SR ', A heterocyclic compound, a phosphine compound, an amino acid derivative, a sugar derivative, and a thiocyano group, which may be the same as or different from each other. Here, R'represents an aliphatic hydrocarbon group, an aryl group, a heterocyclic group, an acyl group, a carbamoyl group, a thiocarbamoyl group, or a sulfonyl group. Q represents a counter anion or counter cation necessary for neutralizing the charge of the compound, x and z represent an integer of 0 to 4, y and p represent 1 or 2, and q represents 0 including a decimal. ~
Represents a value of 1. However, neither x nor z is 0.

The compound represented by formula (I) is preferably a compound in which L ¹ and L ² contain at least one unstable sulfur group capable of reacting with silver halide to form silver sulfide. , Hydantoin compounds, thioether compounds, mesoionic compounds, -SR ', heterocyclic compounds,
Alternatively, it represents a phosphine compound, and x, y, and z each represent 1.

More preferably as the compound represented by the general formula (I), L ¹ and L ² contain at least one labile sulfur group capable of reacting with silver halide to form silver sulfide. Compound, mesoionic compound, or -SR '
And x, y, z, and p each represent 1.

The gold compound represented by formula (I) will be described in more detail below. In the general formula (I), compounds having an unstable sulfur group capable of reacting with silver halides represented by L ¹ and L ² to produce silver sulfide include thioketones (for example, thioureas, Thioamides or rhodanines), thiophosphates, thiosulfates.

The compound containing at least one unstable sulfur group capable of reacting with silver halide to produce silver sulfide is preferably thioketones (preferably thioureas, thioamides, etc.), thiosulfate. Represents a class.

Next, examples of the hydantoin compound represented by L ¹ and L ² in the general formula (I) include unsubstituted hydantoin and N-methylhydantoin, and the thioether compound includes a thio group. Containing 1 to 8
They are substituted or unsubstituted linear or branched alkylene groups (eg, ethylene, triethylene, etc.), or chain or cyclic thioethers linked by a phenylene group (eg, bishydroxyethyl thioether, 3,6).
-Dithia-1,8-octanediol, 1,4,8,1
1-tetrathiacyclotetradecane etc.) and the like,
Examples of mesoionic compounds include mesoionic-3-mercapto-1,2,4-triazoles (for example, mesoionic-1,4,5-trimethyl-3-mercapto-
1,2,4-triazole etc.) and the like.

Next, in the general formula (I), L ¹ and L ² are -S.
When R'is represented, the aliphatic hydrocarbon group represented by R'is a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms (for example, methyl, ethyl, isopropyl, n-propyl). , N-butyl, t-butyl, 2-pentyl, n-hexyl, n-octyl, t-octyl,
2-ethylhexyl, 1,5-dimethylhexyl, n-
Decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, hydroxyethyl, hydroxypropyl, 2,
3-dihydroxypropyl, carboxymethyl, carboxyethyl, sodium sulfoethyl, diethylaminoethyl, diethylaminopropyl, butoxypropyl,
Ethoxyethoxyethyl, n-hexyloxypropyl etc.), a substituted or unsubstituted cyclic alkyl group having 3 to 18 carbon atoms (eg cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, adamantyl, cyclododecyl etc.), 2 to 2 carbon atoms 16 alkenyl groups (eg, allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl groups having 2 to 10 carbon atoms (eg, propargyl, 3
-Pentynyl, etc.), an aralkyl group having 6 to 16 carbon atoms (eg, benzyl, etc.) and the like, and the aryl group includes a substituted or unsubstituted phenyl group having 6 to 20 carbon atoms and a naphthyl group (eg, unsubstituted phenyl). , Unsubstituted naphthyl, 3,5-dimethylphenyl, 4-butoxyphenyl, 4-dimethylaminophenyl, 2-carboxyphenyl and the like), and the heterocyclic group includes, for example, a substituted or unsubstituted nitrogen-containing hetero 5 Membered ring (for example, imidazolyl, 1,2,4-triazolyl, tetrazolyl,
Oxadiazolyl, thiadiazolyl, benzimidazolyl, purinyl, etc.), a substituted or unsubstituted nitrogen-containing hetero 6-membered ring (eg pyridyl, piperidyl, 1,3,5-
Triazino, 4,6-dimercapto-1,3,5-triazino, etc.), a furyl group, or a thienyl group, and the like, and examples of the acyl group include acetyl and benzoyl, and examples of the carbamoyl group include dimethylcarbamoyl. And the like. Examples of the thiocarbamoyl group include diethylthiocarbamoyl and the like, and examples of the sulfonyl group include a substituted or unsubstituted alkylsulfonyl group having 1 to 10 carbon atoms (eg, methanesulfonyl, ethanesulfonyl, etc.), carbon Examples of the substituted or unsubstituted phenylsulfonyl group of the formulas 6 to 16 (eg, phenylsulfonyl and the like) can be mentioned.

Further, as —SR ′ represented by L ¹ and L ² , R ′ is preferably an aryl group or a heterocyclic group, more preferably a heterocyclic group, and further preferably a 5-membered or 6-membered member. Is a nitrogen-containing heterocyclic group, most preferably a nitrogen-containing heterocyclic group substituted with a water-soluble group (eg, sulfo, carboxy, hydroxy, amino, etc.).

In the general formula (I), the heterocyclic compound represented by L ¹ and L ² is a substituted or unsubstituted nitrogen-containing hetero 5-membered ring (for example, pyrroles, imidazoles,
Pyrazoles, 1,2,3-triazoles, 1,2,
4-triazoles, tetrazoles, oxazoles, isoxazoles, isothiazoles, oxadiazoles, thiadiazoles, pyrrolidines, pyrrolines, imidazolidines, imidazolines, pyrazolidines, pyrazolines, hydantoins, etc.) And heterocycles containing the 5-membered ring (indoles, isoindoles, indolizines, indazoles, benzimidazoles, purines, benzotriazoles, carbazoles, tetraazaindenes, benzothiazoles,
Indolines, etc.), substituted or unsubstituted nitrogen-containing 6-membered heterocyclic ring (for example, pyridines, pyrazines, pyrimidines, pyridazines, triazines, thiadiazines,
Piperidine, piperazine, morpholine, etc.), and a heterocycle containing the 6-membered ring (eg, quinoline,
Isoquinolines, phthalazines, naphthyridines, quinoxalines, quinazolines, pteridines, phenaziridines, acridines, phenanthrolines, phenazines, etc.), substituted or unsubstituted furans, substituted or unsubstituted thiophenes, benzothia Zolium etc. are mentioned.

The heterocyclic compound represented by L ¹ and L ² is preferably an unsaturated nitrogen-containing hetero 5- or 6-membered ring, or a heterocycle containing the same, such as pyrroles. Imidazoles, pyrazoles, 1,
2,4-triazoles, oxadiazoles, thiadiazoles, imidazolines, indoles, indolizines, indazoles, benzimidazoles, purines, benzotriazoles, carbazoles, tetraazaindenes, benzothiazoles , Pyridines, pyrazines, pyrimidines, pyridazines, triazines, quinolines, isoquinolines, phthalazines, and the like. Further, heterocyclic compounds known as antifoggants in the art (for example, indazoles , Benzimidazoles, benzotriazoles, tetraazaindenes, etc.) are preferred.

Examples of the phosphine compound represented by L ¹ and L ² in the general formula (I) include an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a heterocyclic group (for example, Pyridyl, etc.), a substituted or unsubstituted amino group (eg, dimethylamino, etc.), and / or an alkyloxy group (eg, methyloxy, ethyloxy, etc.) is substituted, and preferably represents 1 to 1 carbon atoms. 10
And the phosphines substituted with an aryl group having 6 to 12 carbon atoms (eg, triphenylphosphine, triethylphosphine, etc.) and the like.

Further, the mesoionic compound represented by L ¹ and L ² , -SR ', and the heterocyclic compound are unstable sulfur groups capable of reacting with silver halide to produce silver sulfide. It is preferable that (for example, a thioureido group or the like) is substituted.

Further, the compounds represented by L ¹ and L ² in the above general formula (I) may further have a substituent as much as possible, and the substituent is, for example, a halogen atom (eg, ,
Fluorine atom, chlorine atom, bromine atom, etc.), aliphatic hydrocarbon group (eg, methyl, ethyl, isopropyl, n-propyl, t-butyl, n-octyl, cyclopentyl, cyclohexyl, etc.), alkenyl group (eg, allyl, Two
-Butenyl, 3-pentenyl etc.), alkynyl group (eg propargyl, 3-pentynyl etc.), aralkyl group (eg benzyl, phenethyl etc.), aryl group (eg phenyl, naphthyl, 4-methylphenyl etc.),
Heterocyclic groups (eg, pyridyl, furyl, imidazolyl, piperidinyl, morpholyl, etc.), alkyloxy groups (eg, methoxy, ethoxy, butoxy, 2-ethylhexyloxy, ethoxyethoxy, methoxyethoxy, etc.), aryloxy groups (eg, phenoxy) , 2-naphthyloxy, etc.), an amino group (eg, unsubstituted amino,
Dimethylamino, diethylamino, dipropylamino,
Dibutylamino, ethylamino, dibenzylamino, anilino, etc.), acylamino group (eg, acetylamino, benzoylamino, etc.), ureido group (eg, unsubstituted ureido, N-methylureido, N-phenylureido, etc.), thioureido group (For example, unsubstituted thioureido, N-methylthioureido, N-phenylthioureido, etc.), selenouride group (for example, unsubstituted selenouride, etc.), phosphine selenide group (diphenylphosphine selenide, etc.), telluroide group (for example, unsubstituted) Telluroide, etc.), urethane group (eg, methoxycarbonylamino, phenoxycarbonylamino, etc.), sulfonamide group (eg, methylsulfonamide, phenylsulfonamide, etc.), sulfamoyl group (eg, unsubstituted sulfamoyl group) N, N-dimethylsulfamoyl, N-phenylsulfamoyl etc.), carbamoyl group (eg unsubstituted carbamoyl, N, N-diethylcarbamoyl, N-phenylcarbamoyl etc.), sulfonyl group (eg methanesulfonyl, p -Toluenesulfonyl, etc.), a sulfinyl group (eg, methylsulfinyl,
Phenylsulfinyl etc.), alkyloxycarbonyl group (eg methoxycarbonyl, ethoxycarbonyl etc.), aryloxycarbonyl group (eg phenoxycarbonyl etc.), acyl group (eg acetyl, benzoyl, formyl, pivaloyl etc.), acyloxy group ( For example, acetoxy, benzoyloxy and the like), phosphoric acid amide group (for example, N, N-diethylphosphoric acid amide and the like), alkylthio group (for example, methylthio, ethylthio and the like), arylthio group (for example, phenylthio and the like),
Cyano group, sulfo group, thiosulfonic acid group, sulfinic acid group, carboxy group, hydroxy group, mercapto group, phosphono group, nitro group, sulfino group, ammonio group (eg, trimethylammonio, etc.), phosphonio group, hydrazino group, thiazolino Group, a silyloxy group (for example, t-
Butyldimethylsilyloxy, t-butyldiphenylsilyloxy) and the like. When there are two or more substituents, they may be the same or different.

Next, Q and q in the general formula (I) will be described. In the general formula (I), the counter anion represented by Q is a halogenium ion (for example, F ⁻ , Cl ⁻ ,
Br ⁻ , I ⁻ ), tetrafluoroborate ion (B
F ₄ ^-), hexafluorophosphate ion (P
F ₆ ^-), sulfate ion (SO ₄ ^2-), arylsulfonate ions (e.g., p- toluenesulfonate ion,
Naphthalene-2,5-disulfonate ion, etc.), carboxy ion (eg, acetate ion, trifluoroacetate ion, oxalate ion, benzoate ion, etc.) and the like, and the counter cation represented by Q is an alkali metal. Ion (eg, lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion, etc.), alkaline earth metal ion (eg, magnesium ion, calcium ion, etc.), substituted or unsubstituted ammonium ion (eg, unsubstituted ammonium) Ion, triethylammonium, tetramethylammonium, etc.), a substituted or unsubstituted pyridinium ion (eg, unsubstituted pyridinium ion, 4-phenylpyridinium ion, etc.), and a proton. Further, q is the number of Q for neutralizing the charge of the compound, and represents a value of 0 to 1, and the value may be a decimal number.

Preferred as the counter anion represented by Q
Is a halogenium ion (eg Cl ^-, Br^-), Tet
Lafluoroborate ion, hexafluorophosphate
Counter cation represented by Q, which is a toion or a sulfate ion
As the alkali metal ion (for example, nato)
Lithium ion, potassium ion, rubidium ion, cell
Sium ion, etc.), substituted or unsubstituted ammonium
Ions (eg, unsubstituted ammonium ions, triethyl
Lumonium, tetramethylammonium etc.), or
It is a proton.

Specific examples (L- ^{1 to} L-17) of the compound represented by L ¹ or L ² are shown below, but the present invention is not limited thereto. In addition, the numerical value in parentheses shows a logβ ₂ value.

[0062]

[Chemical 1]

[0063]

[Chemical 2]

The compound represented by the general formula (I) can be prepared by a known method, for example, in Organic and Nuclear Chemistry Letters (INORG.NUCL.
CHEM. LETTERSVOL. 10, 641 pages, 1
974), Transition Metal Chemistry (T
positionMet. Chem. Pages 1,248,
1976), Actor Crystallographica (Act)
a. Cryst. B32, p. 3321, 1976),
JP-A-8-69075, JP-B-45-8831, JP-A-915371A1, JP-A-6-11788,
JP-A-6-501789, JP-A-4-267249
And JP-A-9-118685 and the like.

Next, specific examples (S-1 to S-19) of the compound represented by the general formula (I) are shown, but the present invention is not limited thereto.

[0066]

[Chemical 3]

[0067]

[Chemical 4]

[0068]

[Chemical 5]

The gold sensitization in the present invention is usually carried out by adding a gold sensitizer and stirring the emulsion at a high temperature (preferably 40 ° C. or higher) for a certain period of time. The amount of the gold sensitizer added varies depending on various conditions, but as a guide, it is preferably 1 × 10 ^{−7 to} 1 × 10 ⁻⁴ mol per mol of silver halide.

In the present invention, as the gold sensitizer, in addition to the above compounds, a gold compound usually used (eg, chloroauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, Tetracyano auric acid, ammonium aurothiocyanate, pyridyl trichloro gold, etc.) can be used together.

The silver halide emulsion of the present invention can be used in combination with other chemical sensitization besides gold sensitization. As the chemical sensitization method that can be used in combination, sulfur sensitization, selenium sensitization, tellurium sensitization, noble metal sensitization other than gold, or reduction sensitization can be used. As the compound used for the chemical sensitization, those described in JP-A-62-215272, from page 18, lower right column to page 22, upper right column are preferably used.

The silver halide emulsion of the present invention contains various compounds or precursors thereof for the purpose of preventing fog during production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. It can be added.
Specific examples of these compounds are described in JP-A-62-215272.
Those described on pages 39 to 72 of the publication are preferably used. In addition, 5-described in EP 0447647
An arylamino-1,2,3,4-thiatriazole compound (wherein the aryl residue has at least one electron-withdrawing group) is also preferably used.

In the present invention, in order to improve the storage stability of the silver halide emulsion, the hydroxamic acid derivative described in JP-A-11-109576 and JP-A-11-327.
Adjacent to the carbonyl group described in JP-A-094, a cyclic ketone having a double bond in which both ends are substituted with an amino group or a hydroxyl group (particularly represented by the general formula (S1), paragraphs 0036 to 0071 can be incorporated into the specification of the present application.), Sulfo-substituted catechols and hydroquinones described in JP-A No. 11-143011, such as 4,5-dihydroxy-1,3-benzenedisulfonic acid, 2, 5-dihydroxy-1,4-benzenedisulfonic acid, 3,4-dihydroxybenzenesulfonic acid, 2,3-dihydroxybenzenesulfonic acid, 2,5
-Dihydroxybenzenesulfonic acid, 3,4,5-trihydroxybenzenesulfonic acid and salts thereof, etc.),
General formula (A) of US Pat. No. 5,556,741
Hydroxylamines represented by (US Pat. No. 5,555
No. 6,741 column 4, line 56 to column 11, line 22 is preferably applied to the present application and incorporated as a part of the specification of the present application), JP-A-11-1
The water-soluble reducing agents represented by the general formulas (I) to (III) described in JP-A-02045 are preferably used in the present invention.

Further, the silver halide emulsion of the present invention may contain a spectral sensitizing dye for the purpose of imparting so-called spectral sensitivity, which exhibits photosensitivity in a desired light wavelength region.
Examples of the spectral sensitizing dye used for spectral sensitization in the blue, green and red regions include F.I. M. Harter by Heter
ocyclic compounds-Cyanine
dyes and related compound
ds (John Wiley & Sons [Ne
w York, London] 1964). Examples of specific compounds and the spectral sensitization method are described in the above-mentioned JP-A-62-21.
Those described on page 22, upper right column to page 38 of Japanese Patent No. 5272 are preferably used. Further, as a red-sensitive spectral sensitizing dye for silver halide emulsion grains having a particularly high silver chloride content, the spectral sensitizing dyes described in JP-A-3-123340 are stable, have strong adsorption, It is very preferable from the viewpoint of temperature dependence and the like.

The amount of these spectral sensitizing dyes added is in a wide range depending on the case, and is 0.5 per mol of silver halide.
The range of × 10 ^-6 mol to 1.0 × 10 ^-2 mol is preferable.
More preferably, it is in the range of 1.0 × 10 ⁻⁶ mol to 5.0 × 0 ⁻³ mol.

[Silver Halide Photosensitive Material] Next, the silver halide photographic material of the present invention will be described. The silver halide photographic light-sensitive material of the present invention may be black and white or color, but the silver halide emulsion of the present invention is preferably used in the silver halide color photographic light-sensitive material. The silver halide color photographic light-sensitive material (hereinafter sometimes simply referred to as "light-sensitive material") in which the silver halide emulsion of the present invention is preferably used is a silver halide emulsion layer containing a yellow dye-forming coupler on a support. And a silver halide emulsion layer containing a magenta dye-forming coupler and at least one silver halide emulsion layer containing a cyan dye-forming coupler. At least one layer is characterized by containing the silver halide emulsion of the present invention. In the present invention, the silver halide emulsion layer containing the yellow dye-forming coupler as a yellow coloring layer, the silver halide emulsion layer containing the magenta dye-forming coupler as a magenta coloring layer, and the cyan dye-forming coupler. The silver halide emulsion layer thus prepared functions as a cyan coloring layer. The silver halide emulsion contained in each of the yellow color forming layer, the magenta color forming layer and the cyan color forming layer is sensitive to light in wavelength regions different from each other (for example, light in blue region, green region and red region). It is preferable to have

The light-sensitive material of the present invention may have a hydrophilic colloid layer, an antihalation layer, an intermediate layer and a coloring layer, which will be described later, if desired, in addition to the yellow coloring layer, the magenta coloring layer and the cyan coloring layer. Good.

Conventionally known photographic materials and additives can be used in the light-sensitive material of the present invention. For example, a transmissive support or a reflective support can be used as the photographic support. As the transmissive support, a transparent film such as a cellulose nitrate film or polyethylene terephthalate, and further 2,6-naphthalenedicarboxylic acid (NDC)
Polyesters of A) and ethylene glycol (EG), polyesters of NDCA, terephthalic acid and EG, and the like provided with an information recording layer such as a magnetic layer are preferably used. As the reflective support, a reflective support laminated with a plurality of polyethylene layers or polyester layers and containing a white pigment such as titanium oxide in at least one of the water resistant resin layers (laminate layer) is preferable.

Further preferred reflective supports in the present invention include those having a polyolefin layer having fine pores on the paper base on which the silver halide emulsion layer is provided. The polyolefin layer may be composed of multiple layers, in which case the polyolefin layer adjacent to the gelatin layer on the silver halide emulsion layer side preferably has no microvoids (eg polypropylene, polyethylene) and is on a paper substrate. It is more preferable to use a polyolefin (for example, polypropylene or polyethylene) having micropores on the near side. The density of these multi-layer or one-layer polyolefin layers located between the paper substrate and the photographic constituent layers is 0.40 to 40.
It is preferably 1.0 g / ml, and 0.50 to 0.
70 g / ml is more preferred. The thickness of these multi-layer or one-layer polyolefin layers located between the paper substrate and the photographic constituent layers is preferably 10 to 100 μm, and 15 to 100 μm.
70 μm is more preferable. The ratio of the thickness of the polyolefin layer to the thickness of the paper substrate is preferably 0.05 to 0.2,
1 to 0.15 is more preferable.

It is also preferable to provide a polyolefin layer on the opposite side (rear surface) of the above-mentioned paper base from the photographic constituent layers from the viewpoint of increasing the rigidity of the reflective support. In this case, the polyolefin layer on the back surface has a matte surface. Preferred are polyethylene or polypropylene, with polypropylene being more preferred. The polyolefin layer on the back surface is preferably 5 to 50 μm, more preferably 10 to 30 μm, and further has a density of 0.
It is preferably 7 to 1.1 g / ml. Regarding the preferred embodiment of the polyolefin layer provided on the paper substrate in the reflective support of the present invention, see JP-A-10-
No. 333277, No. 10-333278, No. 11-52513, No. 11-65024,
EP0880065 and EP0880066
The examples described in the specification are included.

Further, it is preferable to contain a fluorescent whitening agent in the water resistant resin layer. Also, a hydrophilic colloid layer containing the fluorescent whitening agent dispersed therein may be separately formed. As the fluorescent whitening agent, preferably, a benzoxazole-based, coumarin-based, or pyrazoline-based fluorescent whitening agent can be used, and more preferably, a benzoxazolylnaphthalene-based or benzoxazolyl-stilbene-based fluorescent whitening agent. The amount used is not particularly limited, but preferably 1 to 10
It is 0 mg / m ² . When mixed with a water resistant resin, the mixing ratio is preferably 0.0005 to 3 mass% with respect to the resin.
And more preferably 0.001 to 0.5 mass%.

The reflective type support may be a transmissive type support or the above-mentioned reflective type support coated with a hydrophilic colloid layer containing a white pigment. Further, the reflection type support may be a support having a specular reflection or second-class diffuse reflection metal surface.

The support used in the light-sensitive material of the present invention is a support in which a white polyester support or a layer containing a white pigment is provided on a support having a silver halide emulsion layer for a display. The body may be used. Further, in order to improve the sharpness, it is preferable to apply an antihalation layer on the silver halide emulsion layer-coated side or the back side of the support. Especially, the transmission density of the support is 0.35 to 0.8 so that the display can be viewed with both reflected light and transmitted light.
It is preferable to set in the range of.

In the light-sensitive material of the present invention, a hydrophilic colloid layer can be decolorized by a treatment described in European Patent EP 0,337,490A2, pages 27 to 76 for the purpose of improving image sharpness and the like. Dyes (among others, oxonol dyes) are added so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more, and dihydric alcohols (e.g. 1 part of titanium oxide surface-treated with trimethylolethane)
It is preferable to contain 2 mass% or more (more preferably 14 mass% or more).

In the light-sensitive material of the present invention, a hydrophilic colloid layer is added to the European Patent EP0 for the purpose of preventing irradiation and halation and improving safety of safelight.
337490A2, pages 27-76,
Dyes that can be decolorized by treatment (including oxonol dyes,
Cyanine dye) is preferably added. Furthermore, the dyes described in European Patent EP0819977 are also preferably added to the present invention. Some of these water-soluble dyes may deteriorate color separation and safelight safety when the amount used is increased. Examples of dyes that can be used without deteriorating the color separation include JP-A-5-127324 and JP-A-5-12
The water-soluble dyes described in JP 7325 and JP 5-216185 are preferable.

In the present invention, instead of the water-soluble dye,
Alternatively, a colored layer that can be decolorized by treatment with a water-soluble dye is used. The coloring layer that can be decolorized by the treatment used may be in direct contact with the emulsion layer, or may be arranged so as to be in contact with the emulsion layer via an intermediate layer containing a treatment color mixing inhibitor such as gelatin or hydroquinone. This colored layer is preferably provided in the lower layer (support side) of the emulsion layer that develops a primary color of the same kind as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to selectively install only a part of them. It is also possible to provide a colored layer that is colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is in the wavelength range used for exposure (400 nm for ordinary printer exposure).
It is preferable that the optical density value is 0.2 or more and 3.0 or less at a wavelength having the highest optical density in the visible light region of up to 700 nm, the wavelength of the scanning exposure light source used in the case of scanning exposure). It is more preferably 0.5 or more and 2.5 or less, and particularly preferably 0.8 or more and 2.0 or less.

A conventionally known method can be applied to form the colored layer. For example, the dyes described in JP-A-2-282244, from page 3, upper right column to page 8,
-7931 gazette, page 3, upper right column to page 11, lower left column, a method of incorporating a hydrophilic colloid layer in the form of solid fine particle dispersion, a method of mordanting an anionic dye with a cationic polymer, a dye A method of adsorbing to a fine particle such as silver halide and fixing it in a layer, JP-A-1-239
A method using colloidal silver as described in Japanese Patent No. 544, and the like. As a method for dispersing a fine powder of a pigment in a solid state, for example, a method of containing a fine powder dye that is substantially water-insoluble at least at pH 6 or less, but is substantially water-soluble at least at pH 8 or more is disclosed in Japanese Patent Laid-Open No. 2-308244, pages 4-13. Further, for example, a method of mordanting an anionic dye on a cationic polymer is described on pages 18 to 26 of JP-A-2-84637. For the preparation of colloidal silver as a light absorber, see US Pat. No. 2,688,
601 and 3,459,563. Among these methods, the method of incorporating a fine powder dye and the method of using colloidal silver are preferable.

The silver halide photographic light-sensitive material of the present invention is used as a color negative film, a color positive film, a color reversal film, a color reversal photographic paper, a color photographic paper, etc. Among them, it is preferable to use it as a color photographic paper.
Color photographic paper is a yellow color-forming silver halide emulsion layer,
It is preferable to have at least one magenta color forming silver halide emulsion layer and at least one cyan color forming silver halide emulsion layer. In general, these silver halide emulsion layers are yellow color forming in order from the support. These are a silver halide emulsion layer, a magenta coloring silver halide emulsion layer, and a cyan coloring silver halide emulsion layer.

However, a layer structure different from this may be adopted. The silver halide emulsion layer containing the yellow coupler may be arranged at any position on the support, but when the yellow coupler-containing layer contains silver halide tabular grains, the magenta coupler-containing silver halide It is preferably coated at a position farther from the support than at least one of the emulsion layer and the cyan coupler-containing silver halide emulsion layer. Further, from the viewpoint of accelerating color development, accelerating desilvering, and reducing residual color due to a sensitizing dye, the yellow coupler-containing silver halide emulsion layer is coated at a position farthest from the support as compared with other silver halide emulsion layers. It is preferably provided. Further, from the viewpoint of reducing Blix fading, the cyan coupler-containing silver halide emulsion layer is preferably a central layer of other silver halide emulsion layers, and from the viewpoint of reducing photofading, a cyan coupler-containing silver halide emulsion layer. Is preferably the bottom layer. Further, each of the yellow, magenta and cyan color forming layers may be composed of two layers or three layers. For example, JP-A-4-75055 and 9-1.
As described in 14035, 10-246940, US Pat. No. 5,576,159, etc.,
It is also preferable to provide a coupler layer containing no silver halide emulsion adjacent to the silver halide emulsion layer to form a color forming layer.

The silver halide emulsion and other materials (additives and the like) and photographic constituent layers (layer arrangement and the like) applied in the present invention, and processing methods and processing additions applied to process the light-sensitive material. As the agent, JP-A-62-21
Those described in JP-A-5272, JP-A-2-33144, and European Patent EP0,355,660A2, and particularly those described in European Patent EP0,355,660A2 are preferably used. . Furthermore, JP-A-5-34889 and 4-359249.
No. 4,313753, and No. 4-27034.
4, gazette 5-66527 gazette, and gazette 4-34548.
No. 4, 145,433, No. 2-854, No. 1,158,431, No. 2-90145, No. 3-19439, No. 2-93641, and European Patent Publication No. 0520457A2. The silver halide color photographic light-sensitive material and the processing method therefor described in the specification and the like are also preferable.

Particularly, in the present invention, the above-mentioned reflection type support, silver halide emulsion, different metal ion species doped in silver halide grains, storage stabilizer for silver halide emulsion or antifoggant. , Chemical sensitization method (sensitizer), spectral sensitization method (spectral sensitizer), cyan, magenta, yellow coupler and its emulsion dispersion method, color image storability improving agent (anti-staining agent or anti-fading agent), As for the dye (colored layer), the type of gelatin, the layer structure of the photosensitive material and the coating pH of the photosensitive material, those described in each part of the patent shown in Table 1 below are particularly preferably applicable.

[0092]

[Table 1]

Other cyan, magenta and yellow couplers used in the present invention are disclosed in JP-A-62-62.
-215272, page 91, upper right column, fourth line to 121
Page top left column, line 6, page 3 top right column, line 14 to page 18 top left column, end line, page 30 top right column, line 6 to page 35, bottom right column, line 11 of JP-A-2-33144 EP0355,660
Page 4, lines 15 to 27, page 5, lines 30 to 28, end line, page 45, lines 29 to 31, line 47, lines 23 to 63, line 50 of the A2 specification. The couplers described are also useful. In the present invention, compounds represented by the general formulas (II) and (III) of WO-98 / 33760 and the general formula (D) of JP-A-10-221825 may be added, which is preferable.

As the cyan dye-forming coupler usable in the present invention (sometimes referred to simply as "cyan coupler"), a pyrrolotriazole type coupler is preferably used, and a general formula (I) of JP-A-5-313324 is used. Or a coupler represented by (II) and JP-A-6-347960.
The couplers represented by the general formula (I) in JP-A No. 1993-154, and the exemplary couplers described in these patents are particularly preferable.
Phenol-based and naphthol-based cyan couplers are also preferable, and for example, a cyan coupler represented by the general formula (ADF) described in JP-A-10-333297 is preferable. Cyan couplers other than those mentioned above include European Patent Nos. EP 0488248 and EP 0491197A.
1, a pyrroloazole-type cyan coupler,
2,5-diacylaminophenol couplers described in US Pat. No. 5,888,716, US Pat.
Pyrazoloazole type cyan couplers having an electron-withdrawing group and a hydrogen bonding group at the 6-position described in JP-A-3,183 and JP-A-4,916,051, and particularly, JP-A-8-17
No. 1185, No. 8-311360, No. 8-3
The pyrazoloazole type cyan coupler having a carbamoyl group at the 6-position described in JP-A-39060 is also preferable.

In addition to the diphenylimidazole type cyan couplers described in JP-A-2-33144, 3-hydroxypyridine type cyan couplers described in European Patent EP 0333185A2 (the couplers listed as specific examples among them ( 42) A 4-equivalent coupler having a chlorine-eliminating group to make it a 2-equivalent compound, or a coupler (6)
And (9) are particularly preferable) and cyclic active methylene cyan couplers described in JP-A-64-32260 (coupler examples 3, 8 and 3 listed as specific examples among them).
4 is particularly preferred), European Patent EP 0456226A1
, A pyrrolopyrazole-type cyan coupler described in
The pyrroloimidazole type cyan coupler described in European Patent EP 0484909 can also be used.

Among these cyan couplers, the pyrroloazole type cyan coupler represented by the general formula (I) described in JP-A No. 11-28138 is particularly preferable, and paragraphs 0012 to 0059 of the patent are described. Including the exemplified cyan couplers (1) to (47) are directly applied to the present application and are preferably incorporated as part of the specification of the present application.

The magenta dye-forming coupler used in the present invention (may be simply referred to as "magenta coupler")
As the 5-
Pyrazolone-based magenta couplers and pyrazoloazole-based magenta couplers are used. Among them, secondary or tertiary alkyl groups as described in JP-A-61-65245 in view of hue, image stability, color developability and the like. Is a pyrazolotriazole coupler directly linked to the 2, 3 or 6 position of the pyrazolotriazole ring, a pyrazoloazole coupler containing a sulfonamide group in the molecule as described in JP-A-61-65246, Pyrazoloazole couplers having an alkoxyphenyl sulfonamide ballast group as described in JP-A-61-147254 and 6 as described in EP 226,849A and EP 294,785A. It is preferable to use a pyrazoloazole coupler having an alkoxy group or an aryloxy group at the position. Particularly, as a magenta coupler, JP-A-8-1
Pyrazoloazole couplers represented by General Formula (M-I) described in JP-A No. 22948 are preferable, and paragraph numbers 0009 to 0026 of the patent are directly applied to the present application and are incorporated as a part of the specification of the present application. In addition to this, a pyrazoloazole coupler having a steric hindrance group at both the 3-position and the 6-position described in European Patent Nos. 854384 and 884640 is also preferably used.

Also, a yellow dye-forming coupler (simply,
(In some cases, referred to as “yellow coupler”), in addition to the compounds listed in the above table, European Patent EP04479
No. 69A1, an acylacetamide type yellow coupler having a 3- to 5-membered cyclic structure in the acyl group, a malondianilide type yellow coupler having a cyclic structure described in European Patent No. EP 0482552A1, European Patent No. 953870A1. Specification, No. 95387
1A1, No. 953872A1, No. 953873A1, No. 953874A1, No. 953875A1, etc. described in Pyrrole-2 or 3-yl or indole-2 or 3- Ilcarbonylacetic acid anilide coupler, US Pat. No. 5,
The acylacetamide type yellow coupler having a dioxane structure described in 118,599 is preferably used. Among them, it is particularly preferable to use an acylacetamide type yellow coupler whose acyl group is a 1-alkylcyclopropane-1-carbonyl group and a malondianilide type yellow coupler in which one of the anilide constitutes an indoline ring. These couplers can be used alone or in combination.

The couplers used in the present invention are loadable latex polymers in the presence (or absence) of the high boiling organic solvents described in the table above (eg US Pat.
No. 3,716), or dissolved with a water-insoluble polymer soluble in an organic solvent, and then emulsified and dispersed in a hydrophilic colloid aqueous solution. Water-insoluble and organic solvent-soluble polymers which can be preferably used are described in US Pat. No. 4,857,449, No. 7
Columns to columns 15 and the homopolymers or copolymers described on pages 12 to 30 of International Publication WO88 / 00723 are mentioned. It is more preferable to use a methacrylate-based or acrylamide-based polymer, especially an acrylamide-based polymer in terms of color image stability and the like.

In the present invention, known color mixing inhibitors can be used, and among them, those described in the following patents are preferable. For example, high molecular weight redox compounds described in JP-A-5-333501, WO98 /
No. 33760, U.S. Pat. No. 4,923,787, and other phenidone and hydrazine compounds, JP-A-5-249637 and JP-A-10-28261.
The white couplers described in Japanese Patent No. 5 and German Patent No. 19629142A1 can be used. Further, particularly when the pH of the developing solution is raised to accelerate the development, German Patent No. 19618786A1, European Patent No. 839623A1, European Patent No. 84297.
It is also preferable to use the redox compounds described in Japanese Patent No. 5A1, German Patent 1980846A1 and French Patent No. 2760460A1.

In the present invention, it is preferable to use a compound having a triazine skeleton having a high molar extinction coefficient as the ultraviolet absorber. For example, the compounds described in the following patents can be used. These are preferably added to the photosensitive layer and / or the non-photosensitive layer. For example, JP-A-46-
3335 gazette, the same 55-152776 gazette, Unexamined-Japanese-Patent No. 5 197074, the same 5-232630 gazette,
No. 5-307232, No. 6-211813, No. 8-53427, No. 8-234364, No. 8-239368, No. 9-31067, No. 10-15898, and the same. 10-14757
7 gazette, the same 10-182621 gazette, German Patent No. 1
9739797A, European Patent 711804A
The compounds described in JP-A No. 8-501291 and the like can be used.

As the binder or protective colloid that can be used in the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. As preferable gelatin, heavy metals contained as impurities such as iron, copper, zinc and manganese are preferably 5 ppm or less,
More preferably, it is 3 ppm or less. The amount of calcium contained in the light-sensitive material is preferably 20 mg / m ²
Or less, more preferably 10 mg / m ² or less, and most preferably 5 mg / m ² or less.

In the present invention, in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, a bactericidal / mold-proofing agent as described in JP-A-63-271247 is used. It is preferable to add it. Further, the film pH of the light-sensitive material is preferably 4.0 to 7.0, and more preferably 4.0 to 6.5.

In the present invention, a surfactant can be added to the light-sensitive material from the viewpoints of improving the coating stability of the light-sensitive material, preventing the generation of static electricity, adjusting the charge amount, and the like. Examples of the surfactant include anionic surfactants, cationic surfactants, betaine surfactants and nonionic surfactants, and examples thereof include those described in JP-A-5-333492. The surfactant used in the present invention is preferably a fluorine atom-containing surfactant. Particularly, a fluorine atom-containing surfactant can be preferably used. These fluorine atom-containing surfactants may be used alone or in combination with other conventionally known surfactants, but preferably in combination with other conventionally known surfactants. The amount of these surfactants added to the light-sensitive material is not particularly limited, but is generally 1 × 10 ^{−5 to} 1 g / m ² , and preferably 1 × 10 ⁻⁴ to 1 × 10 ^{−. It is 1} g / m ² , more preferably 1 × 10 ⁻³ to 1 × 10 ⁻² g / m ² .

The light-sensitive material of the present invention can form an image by an exposure step of irradiating light according to image information and a developing step of developing the light-irradiated light-sensitive material. The light-sensitive material of the present invention is used in a cathode ray (CR) in addition to being used in a printing system using an ordinary negative printer.
It is also suitable for the scanning exposure method using T). A cathode ray tube exposure apparatus is simpler and more compact than an apparatus using a laser, and is low in cost. Moreover, the optical axis and color can be easily adjusted. For the cathode ray tube used for image exposure, various light-emitting bodies that emit light in the spectral region are used as necessary. For example, any one of a red light emitting body, a green light emitting body, and a blue light emitting body, or a mixture of two or more thereof is used. The spectral region is not limited to the above red, green, and blue, and a fluorescent substance that emits light in a yellow, orange, violet, or infrared region is also used. In particular, a cathode ray tube that emits white light by mixing these light emitters is often used.

When the light-sensitive material has a plurality of light-sensitive layers having different spectral sensitivity distributions, and the cathode tube also has a phosphor that emits light in a plurality of spectral regions, a plurality of colors are exposed at once, that is, the cathode ray. Image signals of a plurality of colors may be input to the tube to cause the tube surface to emit light. A method of sequentially inputting image signals for each color to sequentially emit light of each color and exposing through a film that cuts colors other than that color (field sequential exposure)
In general, field sequential exposure is preferable for high image quality because a high resolution cathode ray tube can be used.

The light-sensitive material of the present invention comprises a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or a second harmonic emission light source (SHG) in which a solid-state laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal are combined.
A digital scanning exposure method using monochromatic high-density light such as is preferably used. In order to make the system compact and inexpensive, it is preferable to use a semiconductor laser, or a second harmonic generation light source (SHG) which is a combination of a semiconductor laser or a solid-state laser and a nonlinear optical crystal. In particular, it is preferable to use a semiconductor laser in order to design an apparatus that is compact, inexpensive, and has a long life and high stability, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

When using such a scanning exposure light source,
The spectral sensitivity maximum wavelength of the light-sensitive material of the present invention can be arbitrarily set depending on the wavelength of the scanning exposure light source used.
A solid-state laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal can halve the oscillation wavelength of the laser, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the light-sensitive material can be provided in the normal three wavelength regions of blue, green and red. When the exposure time in such scanning exposure is defined as the time for exposing the pixel size when the pixel density is 400 dpi, the preferable exposure time is 10 ⁻⁴ seconds or less, more preferably 10 ⁻⁶ seconds or less.

The silver halide color photographic light-sensitive material of the present invention can be preferably used in combination with the exposure and development system described in the following known materials. Examples of the developing system include an automatic printing and developing system described in JP-A-10-333253, and JP-A-2000.
No. 10206, a photosensitive material conveying device, a recording system including the image reading device described in JP-A-11-215312, color images described in JP-A-11-88619 and JP-A-10-202950. Exposure system consisting of recording method, JP-A-10-210206
A digital photo print system including a remote diagnosis method described in Japanese Patent Publication No. 10-159187, and a photo print system including an image recording apparatus described in Japanese Patent Application No. 10-159187 are listed.

Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in the above table.

When the light-sensitive material of the present invention is exposed to a printer, it is preferable to use the band stop filter described in US Pat. No. 4,880,726. As a result, light color mixture is removed, and color reproducibility is significantly improved. In the present invention, European patent EP 0789270A
As described in No. 1 specification and EP 0789480 A1 specification, a yellow microdot pattern may be pre-exposed and copy regulation may be applied in advance before image information is added.

Processing of the light-sensitive material of the present invention is described in JP-A-2-
207250, page 26, lower right column, line 1 to page 34, upper right column, line 9 and JP-A-4-97355, page 5, upper left column, line 17 to page 18, lower right column, line 20. The treatment materials and treatment methods of are preferably applicable. As the preservative used in this developer, the compounds described in the patents listed in the above table are preferably used.

The present invention is preferably applied to a light-sensitive material having rapid processing suitability. In the case of rapid processing, the color development time is preferably 60 seconds or less, more preferably 50 seconds.
Seconds or less 6 seconds or more, more preferably 30 seconds or less 6 seconds or more. Similarly, the bleach-fixing time is preferably 60 seconds or less,
More preferably 50 seconds or less and 6 seconds or more, more preferably 3
0 seconds or less and 6 seconds or more. The washing or stabilizing time is preferably 150 seconds or less, more preferably 130 seconds or less and 6 seconds or more. The color developing time means the time from the time when the light-sensitive material enters the color developing solution to the time when it enters the bleach-fixing solution in the next processing step. For example, in the case of processing with an automatic processor, etc., the time during which the light-sensitive material is immersed in the color developing solution (so-called in-liquid time) and the light-sensitive material leaves the color developing solution, and bleaching in the next processing step occurs. The total of the time during which it is transported in the air toward the fixing bath (so-called aerial time) is called the color development time. Similarly, the bleach-fixing time means the time from when the light-sensitive material enters the bleach-fixing solution to when it is next washed with water or enters a stabilizing bath. The washing or stabilizing time is the time during which the light-sensitive material is in the washing or stabilizing liquid and is in the liquid for the drying step (so-called in-liquid time).
Say.

The method of developing the light-sensitive material of the present invention after exposure is a conventional method of developing with a developer containing an alkaline agent and a developing agent, or an alkaline solution containing a developing agent in the light-sensitive material and containing no developing agent In addition to a wet method such as a method of developing with an activator solution such as, a heat development method without using a processing solution can be used. In particular, the activator method is a preferable method because the processing solution does not contain a developing agent, so that the processing solution can be easily managed and handled, and that the load at the time of processing the waste solution is small and the environment can be preserved. In the activator method, the developing agent or its precursor incorporated in the light-sensitive material is, for example, JP-A-8-2343.
88, 9-152686, 9-152.
693, 9-21118, 9-16
The hydrazine type compounds described in Japanese Patent No. 0193 are preferable.

Further, a developing method in which the amount of silver coated on the light-sensitive material is reduced and image amplification processing (intensification processing) using hydrogen peroxide is also preferably used. In particular, it is preferable to use this method as an activator method. Specifically, JP-A-8
Image forming methods using an activator solution containing hydrogen peroxide described in JP-A-297354 and JP-A-9-152695 are preferably used. In the activator method, after the treatment with an activator solution, desilvering is usually carried out.However, in the image amplification processing method using a light-sensitive material having a low silver content, desilvering processing is omitted and washing or stabilization processing is simple. Can be done in any way. Further, in the method of reading image information from a light-sensitive material with a scanner or the like, even when a light-sensitive material having a high silver content such as a light-sensitive material for photographing is used,
A processing mode that does not require desilvering processing can be adopted.

The activator solution, desilvering solution (bleaching / fixing solution), water washing and stabilizing solution used in the present invention may be of known materials and known processing methods. Preferably, Research Disclosure Item 3654
4 (September 1994) pp. 536 to 541, JP-A-8-234388 can be used.

[0117]

EXAMPLES The present invention will be described below in greater detail by giving Examples, but the present invention is not limited thereto.

Example 1 [Preparation of silver halide emulsion] (Preparation of emulsion B-1) Lime-treated gelatin 3% aqueous solution 10
00 ml was adjusted to pH 5.5 and pCl 1.7, and an aqueous solution containing 2.12 mol of silver nitrate and an aqueous solution containing 2.2 mol of sodium chloride were added and mixed simultaneously at 66 ° C. while vigorously stirring. From the time of addition of silver nitrate of 80% to the time of 90%, potassium bromide was added with vigorous mixing in an amount of 2 mol% per mol of the finished silver halide. From the time when the addition of silver nitrate was 80% to the time when it was 90%, an aqueous K ₄ [Ru (CN) ₆ ] solution was added in such an amount that the amount of Ru was 3 × 10 ^-5 mol per mol of the finished silver halide. 88 from the point when the addition of silver nitrate is 83%
%, An aqueous solution of K ₂ [IrCl ₆ ] was added in such an amount that the Ir amount became 3 × 10 ⁻⁸ mol per mol of the finished silver halide. When the addition of 90% of silver nitrate was completed, an aqueous potassium iodide solution was added with vigorous mixing so that the amount of I was 0.2 mol% per mol of the finished silver halide. 9 from the point when the addition of silver nitrate was 92%
At the time of 8%, K ₂ [Ir (5-methyl
The aqueous solution of [hiazole) Cl ₅ ] was added in such an amount that the Ir amount was 1 × 10 ⁻⁶ mol per mol of the finished silver halide. After desalting at 40 ° C., 168 g of lime-processed gelatin was added to adjust the pH to 5.5 and pCl1.8. The obtained grains were cubic silver iodobromochloride grains having a sphere-equivalent diameter of 0.75 μm and a coefficient of variation of 11%, which accounted for approximately 10
The silver halide emulsion accounted for 0%. 40 this emulsion
It was dissolved at 0 ° C., sodium thiosulfonate was added at 2 × 10 ⁻⁵ mol per mol of silver halide, sodium thiosulfate pentahydrate as a sulfur sensitizer and (S-
It was aged at 60 ° C. using 2) so as to be optimum. 40
After the temperature was lowered to ℃, sensitizing dye A was added in an amount of 2 per mol of silver halide.
^{X10 -4} mol, sensitizing dye B is 1 x 10 ^-4 mol per mol of silver halide, 1-phenyl-5-mercaptotetrazole is 2 x 10 ^-4 mol per mol of silver halide, 1
-(5-Methylureidophenyl) -5-mercaptotetrazole is 2x10 ^-4 mol per mol of silver halide, and potassium bromide is 2x10 per mol of silver halide.
^-3 mol was added. The emulsion thus obtained was designated as Emulsion B-1.

[0119]

[Chemical 6]

(Preparation of Emulsion G-1) Lime-treated gelatin 3
% Aqueous solution (1000 ml) was adjusted to pH 5.5 and pCl 1.7, and an aqueous solution containing 2.12 mol of silver nitrate and an aqueous solution containing 2.2 mol of sodium chloride were stirred vigorously at 45 ° C.
And mixed at the same time. From the time when the addition of silver nitrate was 80% to the time when it was 90%, the K ₄ [Ru (CN) ₆ ] aqueous solution had a Ru amount of 3 × per mol of the finished silver halide.
An amount of 10 ⁻⁵ mol was added. 83% addition of silver nitrate
From the time point of 1 to 88%, an aqueous solution of K ₂ [IrCl ₆ ] was added in an amount such that the Ir amount was 5 × 10 ⁻⁸ mol per mol of the finished silver halide. Addition of silver nitrate is 9
From the time point of 2% to the time point of 95%, K ₂ [Ir (5
-Methylthiazole) Cl ₅ ] aqueous solution was added, and the amount of Ir was 5 × 10 ⁻⁷ per mol of the finished silver halide.
Molar amounts were added. Furthermore, the addition of silver nitrate is 95%
From the time point of 98% to the time point of K ₂ [Ir (H ₂ O)
Cl ₅ ] aqueous solution was added in an amount such that the Ir amount was 5 × 10 ⁻⁷ mol per mol of the finished silver halide. After desalting at 40 ° C., 168 g of lime-processed gelatin was added to adjust the pH to 5.5 and pCl1.8. The obtained grains were silver halide emulsions in which cubic silver chloride grains having a sphere-equivalent diameter of 0.35 μm and a coefficient of variation of 10% occupied about 100% of the total projected area. This emulsion was dissolved at 40 ° C. and sodium thiosulfonate was added at 2 × 1 per mol of silver halide.
0 ^-5 mol was added and aged for optimal at 60 ° C. using a sodium thiosulfate pentahydrate and a gold sensitizer as a sulfur sensitizer (S-2). After the temperature was lowered to 40 ° C., the sensitizing dye D was 6 × 10 ⁻⁴ mol and the 1-phenyl-5-mercaptotetrazole was 1 mol of silver halide per mol of silver halide.
2 × 10 ^-4 mol per mol, 1- (5-methylureidophenyl) -5-mercaptotetrazole is 8 × 10 ^-4 mol per mol of silver halide, and potassium bromide is 7 × 10 4 per mol of silver halide. ^-3 mol was added. The emulsion thus obtained was designated as Emulsion G-1.

[0121]

[Chemical 7]

(Preparation of Emulsion G-2) Emulsion G-1 was prepared by adding an aqueous potassium iodide solution to an emulsion having an I content of 0.
Emulsions were prepared which differed only in that the amounts to 1 mol% were added with vigorous mixing. The obtained particles have a sphere-equivalent diameter of 0.
It was a silver halide emulsion having a cubic silver iodochloride grain size of 35 μm and a variation coefficient of 10%, which accounted for almost 100% of the total projected area. The emulsion thus obtained was designated as Emulsion G-2.

(Preparation of Emulsion G-3) Emulsion G-1 was prepared by adding silver nitrate from a time point of 80% to a time point of 90%.
Emulsions were prepared which differed only in that potassium bromide was added in an amount of 2 mol% per mol of finished silver halide with vigorous mixing. The obtained particles have a sphere-equivalent diameter of 0.
It was a silver halide emulsion having a cubic silver bromochloride grain size of 35 μm and a variation coefficient of 10%, which accounted for almost 100% of the total projected area. The emulsion thus obtained was designated as Emulsion G-3.

(Preparation of Emulsion G-4) With Emulsion G-1, potassium bromide becomes 2 mol% per mol of the finished silver halide from the time of addition of silver nitrate of 90% to the time of 100%. Emulsions were prepared which differ only in the amounts added with vigorous mixing. The obtained grains were cubic silver bromochloride grains having a spherical equivalent diameter of 0.35 μm and a coefficient of variation of 10%, which accounted for almost 100% of the total projected area of the silver halide emulsion. The emulsion thus obtained was designated as Emulsion G-4.

(Preparation of Emulsion G-5) With Emulsion G-1, potassium bromide becomes 4 mol% per mol of the finished silver halide from the time of addition of silver nitrate of 80% to the time of 100%. Emulsions were prepared which differ only in the amounts added with vigorous mixing. The obtained grains were cubic silver bromochloride grains having a spherical equivalent diameter of 0.35 μm and a coefficient of variation of 10%, which accounted for almost 100% of the total projected area of the silver halide emulsion. The emulsion thus obtained was designated as Emulsion G-5.

(Preparation of Emulsion G-6) Emulsion G-1 was prepared by adding silver nitrate from a time point of 80% to a time point of 90%.
Potassium bromide was added with vigorous mixing in an amount of 2 mol% per mol of finished silver halide, and when the addition of 90% of silver nitrate was completed, an aqueous potassium iodide solution was added to 1 mol of finished silver halide. The amount of I is about 0.
Emulsions were prepared which differed only in that the amounts to 1 mol% were added with vigorous mixing. The obtained particles have a sphere-equivalent diameter of 0.
The silver halide emulsion had a cubic silver iodobromochloride grain size of 35 μm and a coefficient of variation of 10% and occupied approximately 100% of the total projected area. The emulsion thus obtained was designated as Emulsion G-6. The distribution of the bromide and iodide ion concentrations in the depth direction of emulsion G-6 was measured by the etching / TOF-SIMS method. Even when the addition of the iodide salt solution was completed inside the grain, the iodide ion leached out toward the grain surface, had a maximum concentration on the outermost surface, and had a reduced concentration toward the inside.
On the other hand, the bromide ion had a maximum concentration inside the grain. From this, it is considered that the silver bromide-containing phase is formed in layers inside the grain rather than the silver iodide-containing phase.

(Preparation of Emulsion G-7) With Emulsion G-1, potassium bromide becomes 2 mol% per mol of the finished silver halide from the time of addition of silver nitrate of 90% to the time of 100%. The amount of the silver iodide is 90%, and the aqueous potassium iodide solution is mixed vigorously while the amount of I is 0.1 mol% per mol of the finished silver halide. An emulsion was prepared which differed only in the addition. The obtained grains were cubic silver iodobromochloride grains having a spherical equivalent diameter of 0.35 μm and a coefficient of variation of 10%, which accounted for almost 100% of the total projected area of the silver halide emulsion. The emulsion thus obtained was designated as Emulsion G-7. The distribution of the bromide and iodide ion concentrations in the depth direction of emulsion G-7 was measured by the etching / TOF-SIMS method. Even when the addition of the iodide salt solution was completed inside the grain, the iodide ion leached out toward the grain surface, had a maximum concentration on the outermost surface, and had a reduced concentration toward the inside. On the other hand, the concentration of bromide ion gradually decreased from the surface of the grain to the inside thereof as compared with iodide ion. From this, it is considered that the silver bromide-containing phase is formed in layers inside the grain rather than the silver iodide-containing phase.

(Preparation of Emulsion G-8) With Emulsion G-1, potassium bromide becomes 4 mol% per mol of the finished silver halide from the time of addition of silver nitrate of 80% to the time of 100%. The amount of the silver iodide is 90%, and the aqueous potassium iodide solution is mixed vigorously while the amount of I is 0.1 mol% per mol of the finished silver halide. An emulsion was prepared which differed only in the addition. The obtained grains were cubic silver iodobromochloride grains having a spherical equivalent diameter of 0.35 μm and a coefficient of variation of 10%, which accounted for almost 100% of the total projected area of the silver halide emulsion. The emulsion thus obtained was designated as Emulsion G-8. The distribution of the bromide and iodide ion concentrations in the depth direction of Emulsion G-8 was measured by the etching / TOF-SIMS method. Even when the addition of the iodide salt solution was completed inside the grain, the iodide ion leached out toward the grain surface, had a maximum concentration on the outermost surface, and had a reduced concentration toward the inside. On the other hand, the concentration of bromide ion decreased from the surface of the grain to the inside thereof much more slowly than that of iodide ion.
From this, it is considered that the silver bromide-containing phase is formed in layers inside the grain rather than the silver iodide-containing phase.

(Preparation of Emulsion R-1) Lime-treated gelatin 3
% Aqueous solution (1000 ml) was adjusted to pH 5.5 and pCl 1.7, and an aqueous solution containing 2.12 mol of silver nitrate and an aqueous solution containing 2.2 mol of sodium chloride were stirred vigorously at 45 ° C.
And mixed at the same time. From the time of addition of silver nitrate of 80% to the time of 100%, potassium bromide was added with vigorous mixing in an amount of 4 mol% per mol of the finished silver halide. From the time when the addition of silver nitrate was 80% to the time when it was 90%, the K ₄ [Ru (CN) ₆ ] aqueous solution had a Ru amount of 3 × per mol of the finished silver halide.
An amount of 10 ⁻⁵ mol was added. 83% addition of silver nitrate
From the time point of 1 to 88%, an aqueous solution of K ₂ [IrCl ₆ ] was added in an amount such that the Ir amount was 5 × 10 ⁻⁸ mol per mol of the finished silver halide. Addition of silver nitrate is 9
At the end of 0%, an aqueous potassium iodide solution was added with vigorous mixing so that the amount of I was 0.1 mol% per mol of the finished silver halide. 92 addition of silver nitrate
% To 95%, K ₂ [Ir (5-
An aqueous solution of methylthiazole) Cl ₅ ] was added in an amount of 5 × 10 ⁻⁷ mol of Ir per mol of the finished silver halide. Further, from the time when the addition of silver nitrate was 95% to the time when 98% was added, K ₂ [Ir (H ₂ O) C
1 ₅ ] aqueous solution was added in such an amount that the Ir amount became 5 × 10 ⁻⁷ mol per mol of the finished silver halide. After desalting at 40 ° C., add 168 g of lime-processed gelatin,
The pH was adjusted to 5.5 and pCl1.8. The obtained grains were cubic silver iodobromochloride grains having a spherical equivalent diameter of 0.35 μm and a coefficient of variation of 10%, which accounted for almost 100% of the total projected area of the silver halide emulsion. This emulsion was dissolved at 40 ° C. and sodium thiosulfonate was added at 2 × 1 per mol of silver halide.
0 ^-5 mol was added and aged for optimal at 60 ° C. using a sodium thiosulfate pentahydrate and a gold sensitizer as a sulfur sensitizer (S-2). After cooling to 40 ° C., the sensitizing dye H was added to the silver halide at 2 × 10 ⁻⁴ mol and the 1-phenyl-5-mercaptotetrazole was added to the silver halide at 1 mol.
2 × 10 ⁻⁴ mol per mol, 1- (5-methylureidophenyl) -5-mercaptotetrazole 8 × 10 ⁻⁴ mol per mol silver halide, Compound I 1 × 10 ⁻ mol per mol silver halide. ³ mol and potassium bromide were added at 7 × 10 ⁻³ mol per mol of silver halide. The emulsion thus obtained was designated as Emulsion R-1.

[0130]

[Chemical 8]

[0131]

[Chemical 9]

[Preparation of silver halide photographic light-sensitive material] After the corona discharge treatment was applied to the surface of a support having both sides of paper coated with polyethylene resin, a gelatin subbing layer containing sodium dodecylbenzene sulfonate was applied. Further, the photographic constituent layers of the first layer to the seventh layer were sequentially coated to prepare a sample of a silver halide color photographic light-sensitive material having the layer structure shown below. The coating liquid for each photographic constituent layer was prepared as follows.

(Preparation of coating liquid for first layer) 57 g of yellow coupler (ExY), 7 g of color image stabilizer (Cpd-1),
Color image stabilizer (Cpd-2) 4 g, color image stabilizer (Cpd-
3) 7 g and 2 g of color image stabilizer (Cpd-8) as a solvent (So
lv-1) dissolved in 21 g and 80 ml of ethyl acetate, and this solution was emulsified and dispersed in 220 g of a 23.5 mass% gelatin aqueous solution containing 4 g of sodium dodecylbenzenesulfonate by a high-speed stirring emulsifier (dissolver), and water was added. 9
00 g of emulsified dispersion A was prepared. On the other hand, the emulsified dispersion A and the emulsion B-1 were mixed and dissolved to prepare a coating solution for the first layer having the composition described below. The emulsion coating amount indicates a coating amount equivalent to silver.

(Preparation of Coating Solution for Second Layer to Seventh Layer) Coating solutions for the second layer to seventh layer were prepared in the same manner as the coating solution for the first layer. As a gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt (H
-1), (H-2), and (H-3) were used. Further, Ab-1, Ab-2, Ab-3, and Ab-4 were added to each layer in a total amount of 15.0 mg / m ² , 60.0 mg / m ² ,
It was added to a 5.0 mg / m ² and 10.0 mg / m ^2.

[0135]

[Chemical 10]

[0136]

[Chemical 11]

Further, 1-phenyl-5-mercaptotetrazole was added to the green-sensitive emulsion layer and the red-sensitive emulsion layer at 1.0 × 10 ^-3 mol per mol of silver halide, respectively.
It was added so as to be 5.9 × 10 ⁻⁴ mol. Furthermore, 1-phenyl-5 is also used for the second, fourth and sixth layers.
-Mercaptotetrazole, 0.2 mg / m 2 respectively
² , 0.2 mg / m ² and 0.6 mg / m ² were added. Further, for the red-sensitive emulsion layer, a copolymer latex of methacrylic acid and butyl acrylate (mass ratio 1: 1,
Average molecular weight 200000-400000) 0.05 g
/ M ^{2 was} added. Further, the second layer, relative to the fourth layer and the sixth layer, was added disodium catechol-3,5-disulfonate as respectively a ^{6mg / m 2, 6mg / m} 2, 18mg / m 2. In addition, the following dyes (the amount in parentheses represents the coating amount) were added to prevent irradiation.

[0138]

[Chemical 12]

(Layer Structure) The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). Silver halide emulsion,
Indicates the coating amount in terms of silver. Support polyethylene resin laminated paper [white pigment (TiO ₂ ; polyethylene resin on the first layer side;
Content 16% by mass, ZnO; content 4% by mass) and fluorescent whitening agent (4,4′-bis (5-methylbenzoxazolyl) stilbene. Content 0.03% by mass), bluish dye ( Ultramarine)] First layer (blue sensitive emulsion layer) Emulsion B-1 0.24 Gelatin 1.25 Yellow coupler (ExY-1) 0.57 Color image stabilizer (Cpd-1) 0.07 Color image stabilization Agent (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.07 Color image stabilizer (Cpd-8) 0.02 Solvent (Solv-1) 0.21

[0140]   Second layer (color mixing prevention layer)     Gelatin 0.99     Color mixing inhibitor (Cpd-4) 0.09     Color image stabilizer (Cpd-5) 0.018     Color image stabilizer (Cpd-6) 0.13     Color image stabilizer (Cpd-7) 0.01     Solvent (Solv-1) 0.06     Solvent (Solv-2) 0.22

[0141]   Third layer (green sensitive emulsion layer)     Emulsion G-1 0.14     Gelatin 1.36     Magenta coupler (ExM) 0.15     Ultraviolet absorber (UV-A) 0.14     Color image stabilizer (Cpd-2) 0.02     Color image stabilizer (Cpd-4) 0.002     Color image stabilizer (Cpd-6) 0.09     Color image stabilizer (Cpd-8) 0.02     Color image stabilizer (Cpd-9) 0.03     Color image stabilizer (Cpd-10) 0.01     Color image stabilizer (Cpd-11) 0.0001     Solvent (Solv-3) 0.11     Solvent (Solv-4) 0.22     Solvent (Solv-5) 0.20

[0142]   Fourth layer (color mixing prevention layer)     Gelatin 0.71     Color mixing prevention layer (Cpd-4) 0.06     Color image stabilizer (Cpd-5) 0.013     Color image stabilizer (Cpd-6) 0.10     Color image stabilizer (Cpd-7) 0.007     Solvent (Solv-1) 0.04     Solvent (Solv-2) 0.16

[0143]   Fifth layer (red sensitive emulsion layer)     Emulsion R-1 0.12     Gelatin 1.11.     Cyan coupler (ExC-2) 0.13     Cyan coupler (ExC-3) 0.03     Color image stabilizer (Cpd-1) 0.05     Color image stabilizer (Cpd-6) 0.06     Color image stabilizer (Cpd-7) 0.02     Color image stabilizer (Cpd-9) 0.04     Color image stabilizer (Cpd-10) 0.01     Color image stabilizer (Cpd-14) 0.01     Color image stabilizer (Cpd-15) 0.12     Color image stabilizer (Cpd-16) 0.03     Color image stabilizer (Cpd-17) 0.09     Color image stabilizer (Cpd-18) 0.07     Solvent (Solv-5) 0.15     Solvent (Solv-8) 0.05

[0144]   Sixth layer (UV absorption layer)     Gelatin 0.46     UV absorber (UV-B) 0.45     Compound (S1-4) 0.0015     Solvent (Solv-7) 0.25   Seventh layer (protective layer)     Gelatin 1.00     Acrylic modified copolymer of polyvinyl alcohol     (Modification degree 17%) 0.04     Liquid paraffin 0.02     Surfactant (Cpd-13) 0.01

[0145]

[Chemical 13]

[0146]

[Chemical 14]

[0147]

[Chemical 15]

[0148]

[Chemical 16]

[0149]

[Chemical 17]

[0150]

[Chemical 18]

[0151]

[Chemical 19]

[0152]

[Chemical 20]

[0153]

[Chemical 21]

[0154]

[Chemical formula 22]

The sample obtained as described above was used as sample G
-1 was set. Sample G-1 is the emulsion G-1 of the green-sensitive emulsion layer.
Samples in which the emulsions G-2 to G-8 were replaced were prepared in the same manner as samples G-2 to G-8.

The following experiments were conducted to examine the photographic characteristics of these samples. A gradation exposure for sensitometry was applied to each coated sample using a high-illuminance exposure sensitometer (HIE type manufactured by Yamashita Denso Co., Ltd.). Fuji Photo Film Co., Ltd. SP-2 filter is installed, and high illuminance is 10 ^-6.
Exposed for 2 seconds. After the exposure, color development processing A shown below was performed.

The processing steps are shown below. [Processing A] A sample of the above light-sensitive material was processed into a roll having a width of 127 mm, and after imagewise exposure using a mini lab printer processor PP1258AR manufactured by Fuji Photo Film Co., Ltd., the capacity of the color developing tank was doubled in the following processing steps. A continuous process (running test) was performed until replenishment. The treatment using this running liquid was designated as treatment A. Treatment process Temperature Time Replenishment amount ^* Color development 38.5 ° C. 45 seconds 45 ml Bleach fixing 38.0 ° C. 45 seconds 35 ml Rinse (1) 38.0 ° C. 20 seconds-Rinse (2) 38.0 ° C. 20 seconds -Rinse (3) ** 38.0 ° C for 20 seconds-Rinse (4) ** 38.0 ° C for 30 seconds 121 ml * Replenishment amount per 1 m ^{2 of} light-sensitive material ** Rinse screening system RC50D manufactured by Fuji Photo Film Co., Ltd. The rinsing liquid is taken out from the rinsing device (3) and sent to the reverse osmosis membrane module (RC50D) by a pump. The permeated water obtained in the same tank is supplied to the rinse (4), and the concentrated water is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 ml / min, and temperature control circulation was performed for 10 hours a day. (Rinsing was performed from the tank countercurrent system from (1) to (4).)

The composition of each processing solution is as follows. [Color developer] [Tank liquid] [Replenisher] 800 ml water 800 ml Dimethylpolysiloxane-based surfactant 0.1g 0.1g (Silicone KF351A / Shin-Etsu Chemical Co., Ltd.) Tri (isopropanol) amine 8.8g 8.8g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Polyethylene glycol (molecular weight 300) 10.0g 10.0g 4,5-dihydroxybenzene-1,3- Sodium disulfonate 0.5g 0.5g Potassium chloride 10.0g- Potassium bromide 0.040g 0.010g Triazinylaminostilbene fluorescent 2.5g 5.0g Whitening agent (Hakkor FWA-SF / Showa Kagaku) Sodium sulfite 0.1g 0.1g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine                                     8.5g 11.1g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-ami No-4-aminoaniline / 3/2 sulfuric acid monohydrate                                     5.0 g 15.7 g Potassium carbonate 26.3g 26.3g Add water 1000 ml 1000 ml pH (25 ° C / adjusted with potassium hydroxide and sulfuric acid)                                   10.15 12.50

[0159] [Bleach fixer] [Tank solution] [Replenisher] Water 700 ml 600 ml Ethylenediaminetetraacetate Iron (III) ammonium                                   47.0 g 94.0 g Ethylenediaminetetraacetic acid 1.4g 2.8g m-carboxybenzenesulfinic acid                                     8.3g 16.5g Nitric acid (67%) 16.5g 33.0g Imidazole 14.6g 29.2g Ammonium thiosulfate (750 g / l)                           107.0 ml 214.0 ml Ammonium sulfite 16.0 g 32.0 g Ammonium bisulfite 23.1 g 46.2 g Add water 1000 ml 1000 ml pH (adjusted with 25 ℃ / acetic acid and ammonia)                                     6.0 6.0

[0160] [Rinse solution] [Tank solution] [Replenisher] Chlorinated sodium isocyanurate 0.02g 0.02g Deionized water (conductivity 5μS / cm or less)                             1000 ml 1000 ml pH 6.5 6.5

The magenta color density of each sample after the treatment was measured, and a characteristic curve of 10 ⁻⁶ second exposure and high illuminance exposure was obtained. The sensitivity was defined by the reciprocal of the exposure amount that gives a color density 1.5 higher than the minimum color density, and was expressed as a relative value when the sensitivity of Sample G-1 was 100. Further, the gradation was obtained from the slope of the straight line connecting the points of density 1.5 and density 2.0. The results are shown in Table 2.

[0162]

[Table 2]

As is clear from the results of Table 2, the silver iodobromochloride emulsion of the present invention, in which the silver bromide-containing phase and / or the silver iodide-containing phase are respectively formed in layers, is used as a green light-sensitive emulsion layer. It was confirmed that the samples G-2 to G-8 containing the materials had extremely high green sensitivity and high contrast.

Example 2 The sample of Example 1 was changed to the following layer structure to prepare a thin sample. Preparation of Sample First Layer (Blue Sensitive Emulsion Layer) Emulsion B-1 0.14 Gelatin 0.75 Yellow Coupler (ExY-2) 0.34 Color Image Stabilizer (Cpd-1) 0.04 Color Image Stabilizer ( Cpd-2) 0.02 Color image stabilizer (Cpd-3) 0.04 Color image stabilizer (Cpd-8) 0.01 Solvent (Solv-1) 0.13

[0165]   Second layer (color mixing prevention layer)     Gelatin 0.60     Color mixing inhibitor (Cpd-19) 0.09     Color image stabilizer (Cpd-5) 0.007     Color image stabilizer (Cpd-7) 0.007     UV absorber (UV-C) 0.05     Solvent (Solv-5) 0.11

[0166]   Third layer (green sensitive emulsion layer)     Emulsion G-1 0.14     Gelatin 0.73     Magenta coupler (ExM) 0.15     Ultraviolet absorber (UV-A) 0.05     Color image stabilizer (Cpd-2) 0.02     Color image stabilizer (Cpd-7) 0.008     Color image stabilizer (Cpd-8) 0.07     Color image stabilizer (Cpd-9) 0.03     Color image stabilizer (Cpd-10) 0.009     Color image stabilizer (Cpd-11) 0.0001     Solvent (Solv-3) 0.06     Solvent (Solv-4) 0.11     Solvent (Solv-5) 0.06

[0167]   Fourth layer (color mixing prevention layer)     Gelatin 0.48     Color mixing prevention layer (Cpd-4) 0.07     Color image stabilizer (Cpd-5) 0.006     Color image stabilizer (Cpd-7) 0.006     Ultraviolet absorber (UV-C) 0.04     Solvent (Solv-5) 0.09

[0168]   Fifth layer (red sensitive emulsion layer)     Emulsion R-1 0.12     Gelatin 0.59     Cyan coupler (ExC-2) 0.13     Cyan coupler (ExC-3) 0.03     Color image stabilizer (Cpd-7) 0.01     Color image stabilizer (Cpd-9) 0.04     Color image stabilizer (Cpd-15) 0.19     Color image stabilizer (Cpd-18) 0.04     Ultraviolet absorber (UV-7) 0.02     Solvent (Solv-5) 0.09

[0169]   Sixth layer (UV absorption layer)     Gelatin 0.32     Ultraviolet absorber (UV-C) 0.42     Solvent (Solv-7) 0.08   Seventh layer (protective layer)     Gelatin 0.70     Acrylic modified copolymer of polyvinyl alcohol     (Modification degree 17%) 0.04     Liquid paraffin 0.01     Surfactant (Cpd-13) 0.01     Polydimethylsiloxane 0.01     Silicon dioxide 0.003

[0170]

[Chemical formula 23]

The above-mentioned Emulsion G-as the emulsion of the green-sensitive emulsion layer.
The sample using 1 was designated as sample G-21. A sample in which the emulsion G-1 in the green-sensitive emulsion layer was replaced with the emulsion G-8 was prepared in the same manner as the sample G-1 and was designated as sample G-28.

The following experiments were conducted to examine the photographic characteristics of these samples. A gradation exposure for sensitometry was applied to each coated sample using a high-illuminance exposure sensitometer (HIE type manufactured by Yamashita Denso Co., Ltd.). Fuji Photo Film Co., Ltd. SP-2 filter is installed, and high illuminance is 10 ^-6.
Exposed for 2 seconds.

With respect to each of the exposed samples, color development processing was carried out according to the development processing B shown below, and an ultra-rapid processing was performed.

[Processing B] A sample of the above light-sensitive material was set to 127 m.
An image was processed from a negative film of average density to a light-sensitive material sample using an experimental processing device which was processed into a roll of m width, and the processing time and processing temperature were changed to change the mini-lab printer processor PP350 manufactured by Fuji Photo Film Co., Ltd. The same exposure was carried out, and continuous processing (running test) was carried out until the capacity of the color developing replenisher used in the following processing steps became 0.5 times the capacity of the color developing tank.

Processing Steps Temperature Time Replenishment ^* Color development 45.0 ° C. 15 seconds 45 mL Bleach-fix 40.0 ° C. 15 seconds 35 mL Rinse (1) 40.0 ° C. 8 seconds − Rinse (2) 40.0 ° C. 8 seconds − Rinse (3) ** 40.0 ° C. 8 seconds-Rinse (4) 38.0 ° C. 8 seconds 121 mL Dry 80.0 ° C. 15 seconds (Note) * Replenishment amount per 1 m ^{2 of} light-sensitive material ** Fuji Photo Film Co., Ltd. ) The phosphorus screening system RC50D manufactured by the present invention is attached to the rinse (3), and the rinse liquid is taken out from the rinse (3) and sent to the reverse osmosis module (RC50D) by a pump. The permeated water sent in the same tank is supplied to the rinse, and the concentrated liquid is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 mL / min, and the temperature was circulated for 10 hours a day. The rinse was a 4-tank countercurrent system from (1) to (4).

The composition of each processing liquid is as follows. [Color developer] [Tank liquid] [Replenisher] Water 800mL 600mL Optical brightener (FL-1) 5.0 g 8.5 g Triisopropanolamine 8.8g 8.8g Sodium p-toluenesulfonate 20.0 g 20.0 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Sodium sulfite 0.10g 0.50g Potassium chloride 10.0g- 4,5-dihydroxybenzene- Sodium 1,3-disulfonate 0.50 g 0.50 g Disodium-N, N-bis (sulfonate Ethyl) hydroxylamine 8.5 g 14.5 g 4-amino-3-methyl-N-ethyl-N- (Β-methanesulfonamidoethyl) aniline ・ 3/2 Sulfate ・ Monohydrate 10.0g 22.0g Potassium carbonate 26.3g 26.3g Add water to the total volume 1000 mL 1000 mL pH (25 ° C, adjusted with sulfuric acid and KOH) 10.35 12.6

[0177] [Bleach fixer] [Tank solution] [Replenisher] Water 800mL 800mL Ammonium thiosulfate (750 g / mL)                                   107 mL 214 mL Succinic acid 29.5g 59.0g Ethylene diamine tetraammonium iron (III) acetate                                   47.0 g 94.0 g Ethylenediaminetetraacetic acid 1.4g 2.8g Nitric acid (67%) 17.5g 35.0g Imidazole 14.6g 29.2g Ammonium sulfite 16.0 g 32.0 g Potassium metabisulfite 23.1 g 46.2 g Add water to the total volume 1000 mL 1000 mL pH (25 ° C, adjusted with nitric acid and aqueous ammonia) 6.00 6.00

[0178] [Rinse solution] [Tank solution] [Replenisher] Chlorinated sodium isocyanurate 0.02g 0.02g Deionized water (conductivity 5 μS / cm or less) 1000 mL 1000 mL pH (25 ° C) 6.5 6.5

[0179]

[Chemical formula 24]

The magenta color density of each sample after the treatment was measured, and a characteristic curve of 10 ⁻⁶ second exposure and high illuminance exposure was obtained. The sensitivity was defined by the reciprocal of the exposure amount that gives a color density 1.5 higher than the minimum color density, and was expressed as a relative value when the sensitivity of Sample G-1 was 100. Further, the gradation was obtained from the slope of the straight line connecting the points of density 1.5 and density 2.0. Also,
In order to examine the latent image storability, a characteristic curve was obtained when the treatment was started 10 seconds after the exposure in an environment of 20 ° C. and 55% and when the treatment was started 10 minutes after the exposure, and the treatment was performed 10 seconds later. The density change at the exposure dose giving a density of 1.5 when started was examined. To further investigate the exposure temperature / humidity dependency,
Obtain the characteristic curve when the exposure is started in the atmosphere of 10 ° C 55% and after 5 seconds, and when the exposure is started in the atmosphere of 30 ° C and 30% and the treatment is started after 5 seconds, and the exposure is performed in the atmosphere of 10 ° C and 55%. Then, the density change at the exposure amount giving a density of 1.5 when the treatment was started after 5 seconds was examined. These results are shown in Table 3.
It was shown to.

[0181]

[Table 3]

As is clear from the results shown in Table 3, a sample containing a silver iodobromochloride emulsion in which the silver bromide-containing phase and the silver iodide-containing phase of the present invention were respectively formed in layers in a green light-sensitive emulsion layer. G-28 is extremely sensitive to green and has high contrast,
It was confirmed that the latent image storability and exposure temperature / humidity dependency were excellent.

Example 3 The sample of Example 2 was used to form an image by laser scanning exposure. As a laser light source, a wavelength of 430 to 450 nm of a blue semiconductor laser (presented by Nichia at the 48th Joint Lecture on Applied Physics, March 2001) or a semiconductor laser (oscillation wavelength of about 940 nm) is used as a waveguide inversion domain. Structured LiNbO ₃ SHG
About 470 nm obtained by wavelength conversion by a crystal, about 530 nm obtained by wavelength conversion of a semiconductor laser (oscillation wavelength of about 1060 nm) by an SHG crystal of LiNbO ₃ having a waveguide-shaped inversion domain structure, and a red semiconductor laser ( The wavelength of Hitachi type No. HL6738MG) was about 685 nm or the wavelength of a red semiconductor laser (Hitachi type No. HL6501MG) was about 650 nm. The laser light of each of the three colors moves in the direction perpendicular to the scanning direction by the polygon mirror, and
Sequential scanning exposure was made possible. Fluctuations in the amount of light due to the temperature of the semiconductor laser are suppressed by using a Peltier device to keep the temperature constant. The effective beam diameter is 80 μm and the scanning pitch is 42.3 μm (600 d
pi), and the average exposure time per pixel is 1.7.
× 10 ⁻⁷ seconds. After exposure, color development processing B was carried out. As a result of the high illuminance exposure in Example 2, Sample G-28 of the present invention showed high sensitivity and gradation in the green-sensitive layer, and The sample G-28 of the present invention also showed high sensitivity and gradation in the red-sensitive layer, and it was found that both were suitable for image formation using laser scanning exposure.

[0184]

According to the present invention, it is possible to obtain a silver halide emulsion and a silver halide photographic light-sensitive material using the same, which can obtain a highly sensitive and hard gradation even in digital exposure such as laser scanning exposure. it can. Further, according to the present invention, a silver halide emulsion excellent in latent image storability and exposure temperature / humidity dependency and a silver halide photographic light-sensitive material using the same can be obtained. Further, according to the present invention, it is possible to provide a silver halide photographic light-sensitive material which is excellent in rapid processability and can be produced at a low cost due to high coloring efficiency.

─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. ⁷ Identification Code FI Theme Coat (Reference) G03C 1/09 G03C 1/09

Claims (15)

[Claims] 1. A variation coefficient of the sphere-equivalent diameter of all particles is 20% or less, the sphere-equivalent diameter is 0.4 μm or less, the silver bromide-containing phase is formed in a layered form, and the silver chloride-containing phase is contained. Rate is 9
A silver halide emulsion characterized in that 0% by mole or more of silver halide grains account for 50% or more of the total projected area of all the grains. 2. The silver halide emulsion according to claim 1, wherein the silver bromide-containing phase is a silver bromide-containing phase having a maximum silver bromide concentration inside a grain. 3. The variation coefficient of the sphere-equivalent diameter of all grains is 20% or less, the sphere-equivalent diameter is 0.4 μm or less, the silver iodide-containing phase is formed into a layer, and the silver chloride-containing phase is contained. Rate is 9
A silver halide emulsion characterized in that 0% by mole or more of silver halide grains account for 50% or more of the total projected area of all the grains. 4. The silver halide emulsion according to claim 3, wherein the silver iodide-containing phase is a silver iodide-containing phase having a maximum silver iodide concentration on the grain surface. 5. The variation coefficient of the equivalent spherical diameter of all grains is 20% or less, and the equivalent spherical diameter is 0.4 μm or less, and the silver bromide-containing phase and the silver iodide-containing phase are formed in layers. And
A silver halide emulsion characterized in that silver halide grains having a silver chloride content of 90 mol% or more occupy 50% or more of the total projected area of the grains. 6. The silver halide emulsion according to claim 5, wherein the silver bromide-containing phase is formed more inside the grain than the silver iodide-containing phase. 7. The silver halide emulsion according to claim 1, wherein the silver halide grains are cubic or tetradecahedral grains. 8. The silver halide emulsion according to claim 1, wherein the electron slow release time of the silver halide grains is 10 ⁻⁵ to 10 seconds. 9. The silver halide emulsion according to claim 1, wherein the silver halide grains contain a hexacoordinated complex having Cl, Br or I as a ligand and Ir as a central metal. 10. The silver halide emulsion according to claim 9, wherein the hexacoordinated complex is contained in a silver bromide-containing phase. 11. The silver halide emulsion according to claim 1, wherein the silver halide grain contains a hexacoordination complex having Ir as a central metal and having at least one ligand other than halogen and cyan. . 12. The silver halide emulsion according to claim 1, wherein the latent image of the silver halide emulsion has an oxidation potential higher than 70 mV. 13. The silver halide emulsion according to claim 1, wherein the silver halide emulsion is gold sensitized. 14. The silver halide emulsion is gold-sensitized with a gold sensitizer having a colloidal gold sulfide or gold complex stability constant logβ ₂ of 21 or more and 35 or less.
The silver halide emulsion described in 1. 15. A silver halide photographic light-sensitive material comprising the silver halide emulsion according to any one of claims 1 to 14.